Treating compositions comprising polysaccharides

ABSTRACT

The present invention relates to treating compositions, preferably laundry and/or color care compositions comprising polysaccharides, and methods of using such compositions to provide improved color appearance and/or pill prevention and/or abrasion resistance and/or wrinkle resistance and/or shrinkage resistance benefits, while at the same time providing improved cleaning benefits, over laundry and/or fabric and/or color care compositions without such polysaccharides.

This application claims the benefit of Provisional application Ser. No.60/131,287, filed Apr. 27, 1999.

TECHNICAL FIELD

The present invention relates to treating compositions comprising apolysaccharide, and to a method for treating fabrics, natural fibers,such as cellulosic fibers, more particularly cotton, rayon, ramie, jute,flax, linen, polynosic-fibers, Lyocell, poly/cotton, other cotton blendsand mixtures thereof, with such compositions for providing the fabricswith improved color appearance and/or pill prevention and/or abrasionresistance and/or wrinkle resistance and/or shrinkage resistancecompared to treating compositions without such polysaccharides.

BACKGROUND OF THE INVENTION

Consumer desirability for fabric garments that “look like new”, or inother words, fabric garments that retain their “new” appearance,especially with respect to their color appearance has risen.

However, colored garments, especially cotton, rayon and linen garments,have a tendency to wear and show appearance losses. A portion of thiscolor loss may be attributed to abrasion in the laundering process,particularly in automatic washing machines and automatic laundry dryers.

Accordingly, there is a need for treating compositions that provide,refurbish, restore and/or improve the color appearance and/or pillprevention and/or abrasion resistance and/or wrinkle resistance and/orshrinkage resistance of fabrics.

SUMMARY OF THE INVENTION

The present invention is a treating composition comprisingpolysaccharides and a method for imparting color appearance and/or pillprevention and/or abrasion resistance and/or wrinkle resistance and/orshrinkage resistance properties to fabrics such as cotton, rayon, ramie,jute, flax, linen, polynosic-fibers, Lyocell, poly/cotton, other cottonblends and mixtures thereof.

In accordance with one aspect of the present invention, a treatingcomposition comprising polysaccharides is provided.

In accordance with yet another aspect of the present invention, a methodfor treating a fabric in need of treatment comprising contacting thefabric with an effective amount of a polysaccharide-containing treatingcomposition such that the treating composition treats the fabric isprovided.

A preferred treating composition in accordance with the presentinvention comprises one or more polysaccharides and one or more cleaningadjunct materials as described hereinafter, preferably selected from thegroup consisting of builders, bleaching agents, dye transfer inhibitingagents, chelants, dispersants, polysaccharides, softening agents, sudssuppressors, carriers, enzymes, enzyme stabilizing systems, polyacids,soil removal agents, anti-redeposition agents, hydrotropes, opacifiers,antioxidants, bactericides, dyes, perfumes, brighteners and mixturesthereof, and optionally, but preferably further comprising a surfactant.Preferably, the treating composition is in the form of powder orgranules. However, the treating composition may be in the form of aliquid such as an aqueous or non-aqueous heavy duty liquid detergentcomposition, a liquid for spray application, or a solid, such as aconcentrated stick, for rubbing onto the fabric.

Preferably, the treating composition is applied to the fabric throughthe wash and/or through the rinse cycles. However, the treatingcomposition can be applied to the fabric prior to the wash and/or afterthe wash and/or rinse cycles, such as during or prior to ironing, ifneeded.

All percentages and proportions herein are by weight, and all referencescited herein are hereby incorporated by reference, unless otherwisespecifically indicated.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

The treating compositions of the present invention comprise an“effective amount” of a polysaccharide. An “effective amount” of apolysaccharide is any amount capable of measurably improving the colorappearance and/or pill prevention and/or abrasion resistance and/orwrinkle resistance and/or shrinkage resistance properties of a fabricwhen it is washed. In general, this amount may vary quite widely.

“Treating composition(s)” herein is meant to encompass generally laundryand/or fabric care compositions and/or fabric conditioners.

Polysaccharide-Containing Treating Composition

In a preferred embodiment, the treating compositions of the presentinvention comprise an effective amount of one or more polysaccharidesand are preferably free of starch and/or starch derivatives and/orresins. Preferably, the treating compositions further comprise one ormore cleaning adjunct materials. These treating compositions are usefulin the methods of the present invention.

It is desirable that the polysaccharide is present in the treatingcomposition of the present invention in an amount in the range of fromabout 0.01% to about 50% by weight of the treating composition, morepreferably from about 0.5% to about 10% by weight of the treatingcomposition. Furthermore, it is desirable that the polysaccharide ispresent in the wash, soaking and/or spray-treatment solution in amountin the range of from about 2 ppm to about 25000 ppm, more preferablyfrom about 10 ppm to about 5000 ppm.

The treating composition can include conventional detergent ingredients,such as one or more of the following ingredients selected from the groupconsisting of surfactants, builders, bleaches, bleach activators, bleachcatalysts, enzymes, enzyme stabilizing systems, soil release/removalagents, suds suppressors, polyacids, anti-redeposition agents,hydrotropes, opacifiers, antioxidants, bactericides, dyes, perfumes,carriers and brighteners. Examples of such ingredients are generallydescribed in U.S. Pat. No. 5,576,282.

Forms of Compositions

The treating compositions of the present invention can be in solid(powder, granules, bars, tablets), dimple tablets, liquid, paste, gel,spray, stick or foam forms.

The liquid forms can also be in a “concentrated” form which are dilutedto form compositions with the usage concentrations, as givenhereinbelow, for use in the “usage conditions”. Concentratedcompositions comprise a higher level of polysaccharide, typically fromabout 1% to about 99%, preferably from about 2% to about 65%, morepreferably from about 3% to about 25%, by weight of the concentratedtreating composition. Concentrated compositions are used in order toprovide a less expensive product. When a concentrated product is used,i.e., when the polysaccharide is from about 1% to about 99%, by weightof the concentrated composition, it is preferable to dilute thecomposition, preferably with water, before treating a fabric in need oftreatment. Preferably, the water content of the “concentrated” form isless than 40%, more preferably less than 30%, most preferably less than20% by weight of the detergent composition.

The present invention also relates to polysaccharide-containing treatingcompositions incorporated into a spray dispenser to create an article ofmanufacture that can facilitate treatment of fabric articles and/orsurfaces with said compositions containing the polysaccharide and otheroptional ingredients at a level that is effective, yet is notdiscernible when dried on the surfaces. The spray dispenser comprisesmanually activated and non-manual powered (operated) spray means and acontainer containing the treating composition. The articles ofmanufacture preferably are in association with instructions for use toensure that the consumer applies sufficient polysaccharide to providethe desired benefit.

Typical compositions to be dispensed from a sprayer contain a level ofpolysaccharide of from about 0.01% to about 5%, preferably from about0.05% to about 2%, more preferably from about 0.1% to about 1%, byweight of the usage composition.

For wash-added and rinse-added methods, the article of manufacture cansimply comprise a liquid or granular solid polysaccharide-containingtreating composition and a suitable container.

Wash-added compositions, including liquid and granular detergentcompositions and wash additive compositions typically contain a level ofpolysaccharide of from about 0.01% to about 30%, preferably from about0.5% to about 20%, more preferably from about 1% to about 12%, by weightof the wash added compositions.

Typical rinse-added compositions, including liquid fabric conditionerand other rinse additive compositions, contain a level of polysaccharideof from about 0.01% to about 40%, preferably from about 0.3% to about25%, more preferably from about 0.5% to about 25%, most preferably fromabout 1% to about 10%, by weight of the rinse added compositions.

Preferably the articles of manufacture are in association withinstructions for how to use the composition to treat fabrics correctly,to obtain the desirable fabric care results, for example, improved colorappearance and/or pill prevention and/or abrasion resistance and/orwrinkle resistance and/or shrinkage resistance, while at the same timeproviding improved cleaning benefits, including, e.g., the manner and/oramount of composition to be used, and the preferred ways of stretchingand/or smoothing, if any, the fabrics. It is important that theinstructions be as simple and clear as possible. Accordingly, the use ofpictures and/or icons to assist in explaining the instructions isdesirable.

Liquid or solid, preferably powder, polysaccharide-containing treatingcomposition for treating fabric in the rinse step in accordance with thepresent invention comprise an effective amount of the polysaccharide ofthe present invention, and optionally, fabric softener actives, perfume,electrolytes, chlorine scavenging agents, dye transfer inhibitingagents, dye fixative agents, phase stabilizers, chemical stabilizersincluding antioxidants, silicones, antimicrobial actives and/orpreservatives, chelating agents, aminocarboxylate chelating agents,colorants, enzymes, brighteners, soil release agents, anti-encrustationagents, builders and/or mixtures thereof. Again, the composition ispreferably packaged in association with instructions for use to ensurethat the consumer knows what benefits can be achieved.

Yet another liquid or solid, preferably powder or granular, treatingcomposition in accordance with the present invention to be used in thewash cycle comprises an effective amount of one or more polysaccharides,and optionally, surfactants, builders, perfume, chlorine scavengingagents, dye transfer inhibiting agents, dye fixative agents,dispersants, detergent enzymes, heavy metal chelating agents, sudssuppressors, fabric softener actives, chemical stabilizers includingantioxidants, silicones, antimicrobial actives and/or preservatives,soil suspending agents, soil release agents, optical brighteners,colorants, and the like, or mixtures thereof. Again, the composition ispreferably packaged in association with instructions for use to ensurethat the consumer knows what benefits can be achieved.

A preferred treating composition for treating fabric comprises aneffective amount of one or more polysaccharides, and optionally,perfume, fabric lubricants, adjunct fabric shape retention polymers,lithium salts, hydrophilic plasticizers, odor control agents,antimicrobial actives and/or preservatives, surfactants, enzymes, ormixtures thereof. Other optional ingredients can also be added, e.g.,antioxidants, chelating agents, e.g., aminocarboxylate chelating agents,heavy metal chelating agents, antistatic agents, insect and mothrepelling agents, dye transfer inhibiting agents, dye fixative agents,colorants, suds suppressors, and the like, and mixtures thereof. Thecomposition is typically applied to fabric via a, e.g., dipping, soakingand/or spraying process followed by a drying step, including the processcomprising a step of treating or spraying the fabric with the treatingcomposition either outside or inside an automatic clothes dryer followedby, or concurrently with, the drying step in said clothes dryer.However, the composition may be applied by spraying the fabric with thetreating composition prior to and/or during ironing, if needed. Also,the composition may be applied by spraying the fabric during drycleaning. The application can be done industrially by large scaleprocesses on textiles and/or finished garments and clothings, or inconsumer's home by the use of commercial product.

The treating compositions herein can be made by any suitable processknown in the art. Examples of such processes are described in U.S. Pat.No. 5,576,282.

The treating compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between about 6.5 and about 11, preferably between about7.5 and 11. Techniques for controlling pH at recommended usage levelsinclude the use of buffers, alkalis, acids, etc., and are well known tothose skilled in the art.

Non-aqueous based heavy duty laundry detergent compositions containingthe polysaccharide preferably comprise from about 55% to about 98.9% byweight of the detergent composition of a structured,surfactant-containing liquid phase formed by combining:

(a) from about 1% to about 80% by weight of the liquid phase of one ormore non-aqueous organic diluents; and

(b) from about 20% to about 99% by weight of the liquid phase of asurfactant system comprising surfactants selected from the groupconsisting of anionic, nonionic, cationic surfactants and mixturesthereof.

Aqueous based heavy duty laundry detergent compositions containing thepolysaccharide preferably contain a surfactant system comprisingsurfactants selected from the group consisting of nonionic detersivesurfactants, anionic detersive surfactants, zwitterionic detersivesurfactants, amine oxide detersive surfactants and mixtures thereof. Thesurfactant system typically comprises from about 0.01% to about 50%,preferably from about 0.2% to about 30% by weight of the detergentcomposition.

Another appropriate form in which the treating compositions of thepresent invention may be incorporated are tablets. Suchpolysaccharide-containing treating composition tablets comprise aneffective amount of one or more polysaccharides, and optionally,surfactants, builders, perfume, chlorine scavenging agents, dye transferinhibiting agents, dye fixative agents, dispersants, detergent enzymes,heavy metal chelating agents, suds suppressors, fabric softener actives,chemical stabilizers including antioxidants, silicones, antimicrobialactives and/or preservatives, soil suspending agents, soil releaseagents, optical brighteners, colorants, and the like, or mixturesthereof. Again, the composition is preferably packaged in associationwith instructions for use to ensure that the consumer knows whatbenefits can be achieved. The tablets can be used in pre-wash and/orpretreatment procedures as well as through the wash and/or rinse cycles.

Alternatively, the treating compositions of the present invention can beincorporated into a spray dispenser, or concentrated stick form that cancreate an article of manufacture that can facilitate the cleaning and/orfabric care or conditioning of fabric. If the spray treatment is a“pre-treat”, which is followed by a wash cycle, then the spray treatmenttreating compositions preferably comprise from about 0.01% to about 50%of polysaccharide by weight the of total treating composition, morepreferably from about 0.1% to about 3% of polysaccharide by weight ofthe total treating composition. If the spray treatment compositions aredesired to do the cleaning, as in the case of wash, then the spraytreatment compositions preferably comprise from about 2 ppm to about10000 ppm of the polysaccharide by weight of the total treatingcomposition, more preferably from about 200 ppm to about 5000 ppm of thepolysaccharide by weight of the total treating composition. In thelatter case, a brief rinse, not a full wash cycle, is desirable aftertreatment. Such spray treatment compositions are typically packaged in aspray dispenser.

The spray-treatment compositions herein are typically packaged in spraydispensers. The spray dispensers can be any of the manually activatedmeans for producing a spray of liquid droplets as is known in the art,e.g. trigger-type, pump-type, non-aerosol self-pressurized, andaerosol-type spray means. It is preferred that at least about 70%, morepreferably, at least about 80%, most preferably at least about 90% ofthe droplets have a particle size of smaller than about 200 microns.

The spray dispenser can be an aerosol dispenser. Said aerosol dispensercomprises a container which can be constructed of any of theconventional materials employed in fabricating aerosol containers. Thedispenser must be capable of withstanding internal pressure in the rangeof from about 20 to about 110 p.s.i.g., more preferably from about 20 toabout 70 p.s.i.g. The one important requirement concerning the dispenseris that it be provided with a valve member which will permit thetreating compositions of the present invention contained in thedispenser to be dispensed in the form of a spray of very fine, or finelydivided, particles or droplets. A more complete description ofcommercially available suitable aerosol spray dispensers appears in U.S.Pat. No. 3,436,772, Stebbins, issued Apr. 8, 1969; and U.S. Pat. No.3,600,325, Kaufman et al., issued Aug. 17, 1971.

Preferably the spray dispenser is a self-pressurized non-aerosolcontainer having a convoluted liner and an elastomeric sleeve. A morecomplete description of suitable self-pressurized spray dispensers canbe found in U.S. Pat. No. 5,111,971, Winer, issued May 12, 1992; andU.S. Pat. No. 5,232,126, Winer, issued Aug. 3, 1993. Another type ofsuitable aerosol spray dispenser is one wherein a barrier separates thewrinkle reducing composition from the propellant (preferably compressedair or nitrogen), as is disclosed in U.S. Pat. No. 4,260,110, issuedApr. 7, 1981, incorporated herein by reference. Such a dispenser isavailable from EP Spray Systems, East Hanover, N.J.

More preferably, the spray dispenser is a non-aerosol, manuallyactivated, pump-spray dispenser. A more complete disclosure ofcommercially available suitable dispensing devices appears in: U.S. Pat.No. 4,895,279, Schultz, issued Jan. 23, 1990; U.S. Pat. No. 4,735,347,Schultz et al., issued Apr. 5, 1988; and U.S. Pat. No. 4,274,560,Carter, issued Jun. 23, 1981.

Most preferably, the spray dispenser is a manually activatedtrigger-spray dispenser. A more complete disclosure of commerciallyavailable suitable dispensing devices appears in U.S. Pat. No.4,082,223, Nozawa, issued Apr. 4, 1978; U.S. Pat. No. 4,161,288,McKinney, issued Jul. 7, 1985; U.S. Pat. No. 4,434,917, Saito et al.,issued Mar. 6, 1984; and U.S. Pat. No. 4,819,835, Tasaki, issued Apr.11, 1989; U.S. Pat. No. 5,303,867, Peterson, issued Apr. 19, 1994.

A broad array of trigger sprayers or finger pump sprayers are suitablefor use with the compositions of this invention. These are readilyavailable from suppliers such as Calmar, Inc., City of Industry, Calif.;CSI (Continental Sprayers, Inc.), St. Peters, Mo.; Berry Plastics Corp.,Evansville, Ind.—a distributor of Guala® sprayers; or SeaquestDispensing, Cary, Ill.

The preferred trigger sprayers are the blue inserted Guala® sprayer,available from Berry Plastics Corp., the Calmar TS800-1A® sprayers,available from Calmar Inc., or the CSI T7500® available from ContinentalSprayers Inc., because of the fine uniform spray characteristics, sprayvolume and pattern size. Any suitable bottle or container can be usedwith the trigger sprayer, the preferred bottle is a 17 fl-oz. bottle(about 500 ml) of good ergonomics similar in shape to the Cinch® bottle.It can be made of any materials such as high density polyethylene,polypropylene, polyvinyl chloride, polystyrene, polyethyleneterephthalate, glass or any other material that forms bottles.Preferably, it is made of high density polyethylene or polyethyleneterephthalate.

For smaller four fl-oz size (about 118 ml), a finger pump can be usedwith canister or cylindrical bottle. The preferred pump for thisapplication is the cylindrical Euromist II® from Seaquest Dispensing.

It has been found that polysaccharides impart to the fabric improvedcolor appearance and/or pill prevention and/or abrasion resistanceand/or wrinkle resistance and/or shrinkage resistance. These benefitsprovided by the polysaccharide improve the appearance of the fabric.

Methods of Treating

Fabrics, preferably finished garments, can be treated with thepolysaccharide-containing treating compositions by any method known inthe art that accomplishes contacting the fabric with thepolysaccharide-containing treating composition.

A preferred embodiment of the present invention is a method for treatinga fabric in need of treatment, wherein the method comprises contactingthe fabric with an effective amount of polysaccharide-containingtreating composition such that the treating composition treats thefabric.

Preferably, the polysaccharide treating composition is in contact withthe fabric for an “effective amount of time”, which herein meansthe-amount of time required for the polysaccharide-containing treatingcomposition to adequately treat a fabric such that the fabric acquiresimproved color appearance and/or pill prevention and/or abrasionresistance and/or wrinkle resistance and/or shrinkage resistanceproperties. Such time can vary quite widely, however, a preferred rangeof time is from about 5 minutes to about 60 minutes, more preferablyfrom about 10 minutes to about 30 minutes.

Suitable methods include, but are not limited to, washing the fabric ina solution containing the polysaccharide-containing treatingcomposition. The washing can be manual or automatic, such as in awashing machine. The washing machine used in the method described hereincan be any conventional washing machine known in the art. In addition,it can be a specially designed washing machine such as the washingmachine described in U.S. Pat. No. 5,520,025 to Joo et al.

Other suitable methods include, but are not limited to, soaking thefabric in a solution containing the polysaccharide-containing treatingcomposition; spraying the fabric with a solution containing thepolysaccharide-containing treating composition; rubbing the fabric witha solid containing the polysaccharide-containing treating composition;dipping the fabric in a solution containing thepolysaccharide-containing treating composition; rolling thepolysaccharide-containing treating composition onto the fabric,spreading the polysaccharide-containing treating composition onto thefabric and brushing the polysaccharide-containing treating compositiononto the fabric.

In addition to the methods for treating fabrics in need of treatment andother surfaces, described herein, the invention herein also encompassesa laundering pretreatment process for fabrics which have been soiled orstained comprising directly contacting said stains and/or soils with ahighly concentrated form of the polysaccharide-containing treatingcomposition, in any form, preferably a concentrated liquid preferably ina spray dispenser or roll-on device), stick or bar, set forth aboveprior to washing such fabrics using conventional aqueous washingsolutions. Preferably, the cleaning composition remains in contact withthe soil/stain for a period of from about 30 seconds to 24 hours priorto washing the pretreated soiled/stained substrate in conventionalmanner. More preferably, pretreatment times will range from about 1 to180 minutes.

Such methods can be used in industrial applications, such as in thetextile industry, or in residential (domestic) applications, preferably,the methods are used in the residential (domestic) applications.

Further, these methods can be used independently of one another, or canbe combined, concurrently or sequentially.

The use of the treating compositions of the present invention inaccordance with these methods maintains the color appearance and/or pillprevention and/or abrasion resistance and/or wrinkle resistance and/orshrinkage resistance of a fabric in need of treatment through multiplewash cycles.

Product/Instructions

The present invention also encompasses the inclusion of instructions onthe use of the polysaccharide-containing treating compositions with thepackages containing the treating compositions herein or with other formsof advertising associated with the sale or use of the treatingcompositions. The instructions may be included in any manner typicallyused by consumer product manufacturing or supply companies. Examplesinclude providing instructions on a label attached to the containerholding the composition; on a sheet either attached to the container oraccompanying it when purchased; or in advertisements, demonstrations,and/or other written or oral instructions which may be connected to thepurchase of the treating compositions.

The instructions, for instance, may include information relating to thetemperature of the wash water; washing time; recommended settings on thewashing machine; recommended amount of the treating composition to use;pre-soaking procedures; and spray-treatment procedures.

A product comprising a polysaccharide-containing treating composition,the product further including instructions for using the treatingcomposition to treat a fabric in need of treatment, the instructionsincluding the step of: contacting said fabric with an effective amountof said treating composition for an effective amount of time such thatsaid composition treats said fabric.

The product may be a laundry detergent composition, a fabric carecomposition or fabric conditioner. Furthermore, the product may becontained in a spray dispenser.

Polysaccharides

“Polysaccharides” herein is meant natural polysaccharides, and does notinclude polysaccharide derivatives or modified polysaccharides. Suitablepolysaccharides for use in the treating compositions of the presentinvention include, but are not limited to, gums, arabinans, galactans,seeds and mixtures thereof.

Suitable polysaccharides that are useful in the present inventioninclude polysaccharides with a degree of polymerization (DP) over 40,preferably from about 50 to about 100,000, more preferably from about500 to about 50,000, constituting saccharides preferably include, butare not limited to, one or more of the following saccharides:isomaltose, isomaltotriose, isomaltotetraose, isomaltooligosaccharide,fructooligosaccharide, levooligosaccharides, galactooligosaccharide,xylooligosaccharide, gentiooligosaccharides, disaccharides, glucose,fructose, galactose, xylose, mannose, sorbose, arabinose, rhamnose,fucose, maltose, sucrose, lactose, maltulose, ribose, lyxose, allose,altrose, gulose, idose, talose, trehalose, nigerose, kojibiose,lactulose, oligosaccharides, maltooligosaccharides, trisaccharides,tetrasaccharides, pentasaccharides, hexasaccharides, oligosaccharidesfrom partial hydrolysates of natural polysaccharide sources and mixturesthereof.

The polysaccharides can be extracted from plants, produced by organisms,such as bacteria, fungi, prokaryotes, eukaryotes, extracted from animalsand/or humans. For example, xanthan gum can be produced by Xanthomonascampestris, gellan by Sphingomonas paucimobilis, xyloglucan can beextracted from tamarind seed.

The polysaccharides can be linear, or branched in a variety of ways,such as 1-2, 1-3, 104, 1-6, 2-3 and mixtures thereof.

It is desirable that the polysaccharides of the present invention have amolecular weight in the range of from about 10,000 to about 10,000,000,more preferably from about 50,000 to about 1,000,000, most preferablyfrom about 50,000 to about 500,000.

Preferably, the polysaccharide is selected from the group consisting of:tamarind gum (preferably consisting of xyloglucan polymers), guar gum,locust bean gum (preferably consisting of galactomannan polymers), andother industrial gums and polymers, which include, but are not limitedto, Tara, Fenugreek, Aloe, Chia, Flaxseed, Psyllium seed, quince seed,xanthan, gellan, welan, rhamsan, dextran, curdlan, pullulan,scleroglucan, schizophyllan, chitin, hydroxyalkyl cellulose, arabinan(preferably from sugar beets), de-branched arabinan (preferably fromsugar beets), arabinoxylan (preferably from rye and wheat flour),galactan (preferably from lupin and potatoes), pectic galactan(preferably from potatoes), galactomannan (preferably from carob, andincluding both low and high viscosities), glucomannan, lichenan(preferably from icelandic moss), mannan (preferably from ivory nuts),pachyman, rhamnogalacturonan, acacia gum, agar, alginates, carrageenan,chitosan, clavan, hyaluronic acid, heparin, inulin, cellodextrins, andmixtures thereof. These polysaccharides can also be treated (preferablyenzymatically) so that the best fractions of the polysaccharides areisolated.

More preferred polysaccharides have a β-linked backbone.

Xyloglucan polymer is a highly preferred polysaccharide for use in thelaundry and/or fabric care compositions of the present invention.Xyloglucan polymer is preferably obtained from tamarind seedpolysaccharides. The preferred range of molecular weights for thexyloglucan polymer is from about 10,000 to about 1,000,000, morepreferably from about 50,000 to about 200,000.

Polysaccharides, when present, are normally incorporated in the treatingcomposition of the present invention at levels from about 0.1% to about25%, preferably from about 0.2% to about 10% by weight of the treatingcomposition.

Polysaccharides have a high affinity for binding with cellulose. Withoutwishing to be bound by theory, it is believed that the binding efficacyof the polysaccharides to cellulose depends on the type of linkage,extent of branching and molecular weight. The extent of binding alsodepends on the nature of the cellulose (i.e., the ratio of crystallineto amorphous regions in cotton, rayon, linen, etc.).

The natural polysaccharides can be modified with amines (primary,secondary, tertiary), amides, esters, ethers, alcohols, carboxylicacids, tosylates, sulfonates, sulfates, nitrates, phosphates andmixtures thereof. Such a modification can take place in position 2, 3and/or 6 of the glucose unit. Such modified or derivatizedpolysaccharides can be included in the compositions of the presentinvention in addition to the natural polysaccharides.

Nonlimiting examples of such modified polysaccharides include: carboxyland hydroxymethyl substitutions (e.g., glucuronic acid instead ofglucose); amino polysaccharides (amine substitution, e.g., glucosamineinstead of glucose); C₁-C₆ alkylated polysaccharides; acetylatedpolysaccharide ethers; polysaccharides having amino acid residuesattached (small fragments of glycoprotein); polysaccharides containingsilicone moieties. Suitable examples of such modified polysaccharidesare commercially available from Carbomer and include, but are notlimited to, amino alginates, such as hexanediamine alginate, aminefunctionalized cellulose-like O-methyl-(N-1,12-dodecanediamine)cellulose, biotin heparin, carboxymethylated dextran, guarpolycarboxylic acid, carboxymethylated locust bean gum, caroxymethylatedxanthan, chitosan phosphate, chitosan phosphate sulfate,diethylaminoethyl dextran, dodecylamide alginate, sialic acid,glucuronic acid, galacturonic acid, mannuronic acid, guluronic acid,N-acetylglucosamine, N-acetylgalactosamine, and mixtures thereof.

The polysaccharide polymers can be linear, like inhydroxyalkylcellulose, the polymer can have an alternating repeat likein carrageenan, the polymer can have an interrupted repeat like inpectin, the polymer can be a block copolymer like in alginate, thepolymer can be branched like in dextran, the polymer can have a complexrepeat like in xanthan. Descriptions of the polymer definitions are givein “An introduction to Polysaccharide Biotechnology”, by M>Tombs and S.E. Harding, T.J. Press 1998.

Oligosaccharides

The compositions of the present invention may include oligosaccharides.Suitable oligosaccharides that are useful in the present inventioninclude oligosaccharides with a degree of polymerization (DP) of lessthan 20, preferably from about 1 to about 15, more preferably from about2 to about 10, constituting monosaccharides preferably include, but arenot limited to, one or more of the following monosaccharides: glucose,fructose, galactose, xylose, mannose, arabinose, rhamnose, ribose,lyxose, allose, altrose, gulose, idose, talose, and/or theirderivatives. Preferred oligosaccharides have a molecular weight in therange of from about 300 to about 8000. Branched oligosaccharides arepreferred over linear oligosaccharides.

Nonlimiting examples of suitable oligosaccharides can be obtainedcommercially from any of the suppliers—Carbomer(fructo-oligosaccharides, levo-oligosaccharides, inulin, dextra 5000,cellosaccharides, etc.,), Grain Processing Corporation (maltodextrin),Pharmacica Biotech (Dextran series), Palatinit (isomalt) and ShowaSangyo (Isomalto-500).

Oligosaccharides, when present, are normally incorporated in thecleaning composition at levels from about 1% to about 25%, preferablyfrom about 2% to about 10% by weight of the laundry and/or fabric carecomposition.

Cleaning Adjunct Materials

The treating compositions of the present invention comprise an effectiveamount of the polysaccharide, and preferably one or more of theabove-described preferred ingredients, and optionally one or more of thefollowing conventional cleaning adjunct materials either to improve theperformance of the polysaccharide, e.g., in the areas of wrinklecontrol, anti-wear, soil release, tensile strength and the like, or toprovide additional benefits, such as odor control, antimicrobial, andthe like. The useful optional cleaning adjunct materials are those thatare compatible with the polysaccharide, in that they do not interfereand/or substantially or significantly diminish the benefits provided bythe polysaccharide. The precise nature of these optional cleaningadjunct materials, and levels of incorporation thereof will depend onthe physical form of the treating compositions, and the nature of thecleaning operation for which it is to be used.

Examples of such cleaning adjunct materials include, but are not limitedto, the following.

Surfactant System—Detersive surfactants can be, and preferably areincluded in the treating compositions of the present invention. Whenpresent, surfactants comprise at least 0.01%, preferably at least about0.1%, more preferably at least about 0.5%, most preferably at leastabout 1% to about 60%, more preferably to about 35%, most preferably toabout 30% by weight of the treating composition depending upon theparticular surfactants used and the desired effects.

The detersive surfactant can be nonionic, anionic, ampholytic,zwitterionic, cationic, semi-polar nonionic, and mixtures thereof,nonlimiting examples of which are disclosed in U.S. Pat. Nos. 5,707,950and 5,576,282. Preferred treating compositions comprise anionicdetersive surfactants or mixtures of anionic surfactants with othersurfactants, especially nonionic surfactants.

Anionic surfactants are highly preferred for use with the treatingcompositions of the present invention.

Nonlimiting examples of surfactants useful herein include theconventional C₁₁-C₁₈ alkyl benzene sulfonates and primary, secondary andrandom alkyl sulfates, the C₁₀-C₁₈ alkyl alkoxy sulfates, the C₁₀-C₁₈alkyl polyglycosides and their corresponding sulfated polyglycosides,C₁₂-C₁₈ alpha-sulfonated fatty acid esters, C₁₂-C₁₈ alkyl and alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy),C₁₂-C₁₈ betaines and sulfobetaines (“sultaines”), C₁₀-C₁₈ amine oxides,and the like. Other conventional useful surfactants are listed instandard texts.

The surfactant is preferably formulated to be compatible with enzyme andbleaching components, if any, present in the composition. In liquid orgel compositions the surfactant is most preferably formulated such thatit promotes, or at least does not degrade, the stability of any enzymein these compositions.

Nonionic Surfactants—Polyethylene, polypropylene, and polybutylene oxidecondensates of alkyl phenols are suitable for use as the nonionicsurfactant of the surfactant systems of the present invention, with thepolyethylene oxide condensates being preferred. Commercially availablenonionic surfactants of this type include Igepal™ CO-630, marketed bythe GAF Corporation; and Triton™ X45, X-114, X-100 and X-102, allmarketed by the Rohm & Haas Company. These surfactants are commonlyreferred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).

The condensation products of primary and secondary aliphatic alcoholswith from about 1 to about 25 moles of ethylene oxide are suitable foruse as the nonionic surfactant of the nonionic surfactant systems of thepresent invention. Examples of commercially available nonionicsurfactants of this type include Tergitol™ 15-S-9 (the condensationproduct of C₁₁-C₁₅ linear alcohol with 9 moles ethylene oxide),Tergitol™ 24-L-6 NMW (the condensation product of C₁₂-C₁₄ primaryalcohol with 6 moles ethylene oxide with a narrow molecular weightdistribution), both marketed by Union Carbide Corporation; Neodol™ 45-9(the condensation product of C₁₄-C₁₅ linear alcohol with 9 moles ofethylene oxide), Neodol™ 23-3 (the condensation product of C₁₂-C₁₃linear alcohol with 3.0 moles of ethylene oxide), Neodol™ 45-7 (thecondensation product of C₁₄-C₁₅ linear alcohol with 7 moles of ethyleneoxide), Neodol™ 45-5 (the condensation product of C₁₄-C₁₅ linear alcoholwith 5 moles of ethylene oxide) marketed by Shell Chemical Company,Kyro™ EOB (the condensation product of C₁₃-C₁₅ alcohol with 9 molesethylene oxide), marketed by The Procter & Gamble Company, and GenapolLA O30 or O50 (the condensation product of C₁₂-C₁₄ alcohol with 3 or 5moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB inthese products is from 8-11 and most preferred from 8-10.

Also useful as the nonionic surfactant of the surfactant systems of thepresent invention are the alkylpolysaccharides disclosed in U.S. Pat.No. 4,565,647.

Preferred alkylpolyglycosides have the formula:R²O(C_(n)H_(2n)O)_(t)(glycosyl)_(x) wherein R² is selected from thegroup consisting of alkyl, alkylphenyl, hydroxyalkyl,hydroxyalkylphenyl, and mixtures thereof in which the alkyl groupscontain from about 10 to about 18, preferably from about 12 to about 14,carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,preferably 0; and x is from about 1.3 to about 10, preferably from about1.3 to about 3, most preferably from about 1.3 to about 2.7.

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol arealso suitable for use as the additional nonionic surfactant systems ofthe present invention. Examples of compounds of this type includecertain of the commercially-available Plurafac™ LF404 and Pluronic™surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionicsurfactant system of the present invention, are the condensationproducts of ethylene oxide with the product resulting from the reactionof propylene oxide and ethylenediamine. Examples of this type ofnonionic surfactant include certain of the commercially availableTetronic™ compounds, marketed by BASF.

Preferred for use as the nonionic surfactant of the surfactant systemsof the present invention are polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphaticalcohols with from about 1 to about 25 moles of ethylene oxide,alkylpolysaccharides, and mixtures thereof. Most preferred are C₈-C₁₄alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C₈-C₁₈alcohol ethoxylates (preferably C₁₀ avg.) having from 2 to 10 ethoxygroups, and mixtures thereof.

Highly preferred nonionic surfactants are polyhydroxy fatty acid amidesurfactants of the formula: R²—C(O)—N(R¹)—Z wherein R¹ is H, or R¹ isC₁-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixturethereof, R² is C₅₋₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbylhaving a linear hydrocarbyl chain with at least 3 hydroxyls directlyconnected to the chain, or an alkoxylated derivative thereof.Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl or C₁₆₋₁₈ alkylor alkenyl chain such as coconut alkyl or mixtures thereof, and Z isderived from a reducing sugar such as glucose, fructose, maltose,lactose, in a reductive amination reaction.

Anionic Surfactants—Suitable anionic surfactants to be used are linearalkyl benzene sulfonate, alkyl ester sulfonate surfactants includinglinear esters of C₈-C₂₀ carboxylic acids (i.e., fatty acids) which aresulfonated with gaseous SO₃ according to “The Journal of the AmericanOil Chemists Society”, 52 (1975), pp. 323-329. Suitable startingmaterials would include natural fatty substances as derived from tallow,palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplications, comprise alkyl ester sulfonate surfactants of thestructural formula:

wherein R³ is a C₈-C₂₀ hydrocarbyl, preferably an alkyl, or combinationthereof, R⁴ is a C₁-C₆ hydrocarbyl, preferably an alkyl, or combinationthereof, and M is a cation which forms a water soluble salt with thealkyl ester sulfonate. Suitable salt-forming cations include metals suchas sodium, potassium, and lithium, and substituted or unsubstitutedammonium cations, such as monoethanolamine, diethanolamine, andtriethanolamine. Preferably, R³ is C₁₀-C₁₆ alkyl, and R⁴ is methyl,ethyl or isopropyl. Especially preferred are the methyl ester sulfonateswherein R³ is C₁₀-C₁₆ alkyl.

Other suitable anionic surfactants include the alkyl sulfate surfactantswhich are water soluble salts or acids of the formula ROSO₃M wherein Rpreferably is a C₁₀-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkylhaving a C₁₀-C₂₀ alkyl component, more preferably a C₁₂-C₁₈ alkyl orhydroxyalkyl, and M is H or a cation. Typically, alkyl chains of C₁₂-C₁₆are preferred for lower wash temperatures (e.g. below about 50° C.) andC₁₆₋₁₈ alkyl chains are preferred for higher wash temperatures (e.g.above about 50° C.).

Other anionic surfactants useful for detersive purposes include salts ofsoap, C₈-C₂₂ primary of secondary alkanesulfonates, C₈-C₂₄olefinsulfonates, sulfonated polycarboxylic acids prepared bysulfonation of the pyrolyzed product of alkaline earth metal citrates,e.g., as described in British patent specification No. 1,082,179, C₈-C₂₄alkylpolyglycolethersulfates (containing up to 10 moles of ethyleneoxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fattyoleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates,paraffin sulfonates, alkyl phosphates, isethionates such as the acylisethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,monoesters of sulfosuccinates (especially saturated and unsaturatedC₁₂-C₁₈ monoesters) and diesters of sulfosuccinates (especiallysaturated and unsaturated C₆-C₁₂ diesters), acyl sarcosinates, sulfatesof alkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), branched primaryalkyl sulfates, and alkyl polyethoxy carboxylates such as those of theformula RO(CH₂CH₂O)_(k)—CH₂COO—M+ wherein R is a C₈-C₂₂ alkyl, k is aninteger from 1 to 10, and M is a soluble salt-forming cation. Resinacids and hydrogenated resin acids are also suitable, such as rosin,hydrogenated rosin, and resin acids and hydrogenated resin acids presentin or derived from tall oil.

Further examples are described in “Surface Active Agents and Detergents”(Vol. I and II by Schwartz, Perry and Berch). A variety of suchsurfactants are also generally disclosed in U.S. Pat. No. 3,929,678,issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line 58 throughColumn 29, line 23 (herein incorporated by reference).

Highly preferred anionic surfactants include alkyl alkoxylated sulfatesurfactants hereof are water soluble salts or acids of the formulaRO(A)_(m)SO3M wherein R is an unsubstituted C₁₀-C₂₄ alkyl orhydroxyalkyl group having a C₁₀-C₂₄ alkyl component, preferably aC₁₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈ alkyl orhydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,typically between about 0.5 and about 6, more preferably between about0.5 and about 3, and M is H or a cation which can be, for example, ametal cation (e.g., sodium, potassium, lithium, calcium, magnesium,etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylatedsulfates as well as alkyl propoxylated sulfates are contemplated herein.Specific examples of substituted ammonium cations include methyl-,dimethyl, trimethyl-ammonium cations and quaternary ammonium cationssuch as tetramethyl-ammonium and dimethyl piperdinium cations and thosederived from alkylamines such as ethylamine, diethylamine,triethylamine, mixtures thereof, and the like. Exemplary surfactants areC₁₂-C₁₈ alkyl polyethoxylate (1.0) sulfate (C₁₂-C₁₈E(1.0)M), C₁₂-C₁₈alkyl polyethoxylate (2.25) sulfate (C₁₂-C₁₈E(2.25)M), C₁₂-C₁₈ alkylpolyethoxylate (3.0) sulfate (C₁₂-C₁₈E(3.0)M), and C₁₂-C₁₈ alkylpolyethoxylate (4.0) sulfate (C₁₂-Cl₈E(4.0)M), wherein M is convenientlyselected from sodium and potassium.

When included therein, the treating compositions of the presentinvention typically comprise from about 1%, preferably from about 3% toabout 40%, preferably about 20% by weight of such anionic surfactants.

Cationic Surfactants—Cationic detersive surfactants suitable for use inthe treating compositions of the present invention are those having onelong-chain hydrocarbyl group. Examples of such cationic surfactantsinclude the ammonium surfactants such as alkyltrimethylammoniumhalogenides, and those surfactants having the formula:[R²(OR³)_(y)][R⁴(OR³)_(y)]₂R⁵N+X— wherein R² is an alkyl or alkyl benzylgroup having from about 8 to about 18 carbon atoms in the alkyl chain,each R³ is selected from the group consisting of —CH₂CH₂—, —CH₂CH(CH₃)—,—CH₂CH(CH₂OH)—, —CH₂CH₂CH₂—, and mixtures thereof; each R⁴ is selectedfrom the group consisting of C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzylring structures formed by joining the two R⁴ groups,—CH₂CHOH—CHOHCOR⁶CHOHCH₂OH wherein R⁶ is any hexose or hexose polymerhaving a molecular weight less than about 1000, and hydrogen when y isnot 0; R⁵ is the same as R⁴ or is an alkyl chain wherein the totalnumber of carbon atoms of R² plus R⁵ is not more than about 18; each yis from 0 to about 10 and the sum of the y values is from 0 to about 15;and X is any compatible anion.

Highly preferred cationic surfactants are the water-soluble quaternaryammonium compounds useful in the present composition having the formula(i): R₁R₂R₃R₄N⁺X⁻ wherein R₁ is C₈-C₁₆ alkyl, each of R₂, R₃ and R₄ isindependently C₁-C₄ alkyl, C₁-C₄ hydroxy alkyl, benzyl, and—(C₂H₄₀)_(x)H where x has a value from 2 to 5, and X is an anion. Notmore than one of R₂, R₃ or R₄ should be benzyl. The preferred alkylchain length for R₁ is C₁₂-C₁₅ particularly where the alkyl group is amixture of chain lengths derived from coconut or palm kernel fat or isderived synthetically by olefin build up or OXO alcohols synthesis.Preferred groups for R₂R₃ and R₄ are methyl and hydroxyethyl groups andthe anion X may be selected from halide, methosulfate, acetate andphosphate ions.

Examples of suitable quaternary ammonium compounds of formulae (i) foruse herein are include, but are not limited to: coconut trimethylammonium chloride or bromide; coconut methyl dihydroxyethyl ammoniumchloride or bromide; decyl triethyl ammonium chloride; decyl dimethylhydroxyethyl ammonium chloride or bromide; C₁₂₋₁₅ dimethyl hydroxyethylammonium chloride or bromide; coconut dimethyl hydroxyethyl ammoniumchloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryldimethyl benzyl ammonium chloride or bromide; lauryl dimethyl(ethenoxy)₄ ammonium chloride or bromide; choline esters (compounds offormula (i) wherein R₁ is

and di-alkyl imidazolines [(i)].

Other cationic surfactants useful herein are also described in U.S. Pat.No. 4,228,044, Cambre, issued Oct. 14, 1980 and in European PatentApplication EP 000,224.

When included therein, the treating compositions of the presentinvention typically comprise from about 0.2%, preferably from about 1%to about 25%, preferably to about 8% by weight of such cationicsurfactants.

Ampholytic Surfactants—Ampholytic surfactants, examples of which aredescribed in U.S. Pat. No. 3,929,678, are also suitable for use in thetreating compositions of the present invention.

When included therein, the treating compositions of the presentinvention typically comprise from about 0.2%, preferably from about 1%to about 15%, preferably to about 10% by weight of such ampholyticsurfactants.

Zwitterionic Surfactants—Zwitterionic surfactants, examples of which aredescribed in U.S. Pat. No. 3,929,678, are also suitable for use in thetreating compositions of the present invention.

When included therein, the treating compositions of the presentinvention typically comprise from about 0.2%, preferably from about 1%to about 15%, preferably to about 10% by weight of such zwitterionicsurfactants.

Semi-polar Nonionic Surfactants—Semi-polar nonionic surfactants are aspecial category of nonionic surfactants which include water-solubleamine oxides having the formula:

wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixturesthereof containing from about 8 to about 22 carbon atoms; R⁴ is analkylene or hydroxyalkylene group containing from about 2 to about 3carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ isan alkyl or hydroxyalkyl group containing from about 1 to about 3 carbonatoms or a polyethylene oxide group containing from about 1 to about 3ethylene oxide groups (the R⁵ groups can be attached to each other,e.g., through an oxygen or nitrogen atom, to form a ring structure);water-soluble phosphine oxides containing one alkyl moiety of from about10 to about 18 carbon atoms and 2 moieties selected from the groupconsisting of alkyl groups and hydroxyalkyl groups containing from about1 to about 3 carbon atoms; and water-soluble sulfoxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and a moietyselected from the group consisting of alkyl and hydroxyalkyl moieties offrom about 1 to about 3 carbon atoms.

The amine oxide surfactants in particular include C₁₀-C₁₈ alkyl dimethylamine oxides and C₈-C₁₂ alkoxy ethyl dihydroxy ethyl amine oxides.

When included therein, the treating compositions of the presentinvention typically comprise from about 0.2%, preferably from about 1%to about 15%, preferably to about 10% by weight of such semi-polarnonionic surfactants.

Cosurfactants—The treating compositions of the present invention mayfurther comprise a cosurfactant selected from the group of primary ortertiary amines. Suitable primary amines for use herein include aminesaccording to the formula R₁NH₂ wherein R₁ is a C₆-C₁₂, preferably C₆-C₁₀alkyl chain or R₄X(CH₂)_(n), X is —O—, —C(O)NH— or —NH—, R₄ is a C₆-C₁₂alkyl chain n is between 1 to 5, preferably 3. R₁ alkyl chains may bestraight or branched and may be interrupted with up to 12, preferablyless than 5 ethylene oxide moieties.

Preferred amines according to the formula herein above are n-alkylamines. Suitable amines for use herein may be selected from1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Otherpreferred primary amines include C8-C10 oxypropylamine,octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amidopropylamine and amido propylamine. The most preferred amines for use inthe compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine,1-dodecylamine. Especially desirable are n-dodecyldimethylamine andbishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated,lauryl amido propylamine and cocoamido propylamine.

LFNIs—Low foaming nonionic surfactants (LFNI) which are described inU.S. Pat. Nos. 5,705,464 and 5,710,115 can be included in the treatingcompositions of the present invention. LFNI may be present in amountsfrom 0.01% to about 10% by weight, preferably from about 0.1% to about10%, and most preferably from about 0.25% to about 4%. LFNIs are mosttypically used in automatic dishwashing detergent compositions (ADDs) onaccount of the improved water-sheeting action (especially from glass)which they confer to the ADD product. They also encompass non-silicone,nonphosphate polymeric materials further illustrated hereinafter whichare known to defoam food soils encountered in automatic dishwashing.

Preferred LFNIs include nonionic alkoxylated surfactants, especiallyethoxylates derived from primary alcohols, and blends thereof with moresophisticated surfactants, such as thepolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers as described in U.S. Pat. Nos. 5,705,464 and 5,710,115.

LFNIs which may also be used include those POLY-TERGENT® SLF-18 nonionicsurfactants from Olin Corp., and any biodegradable LFNI having themelting point properties discussed hereinabove.

These and other nonionic surfactants are well known in the art, beingdescribed in more detail in Kirk Othmer's Encyclopedia of ChemicalTechnology, 3rd Ed., Vol. 22, pp. 360-379, “Surfactants and DetersiveSystems”, incorporated by reference herein.

Bleaching System—The treating compositions of the present invention maycomprise a bleaching system. Bleaching systems typically comprise a“bleaching agent” (source of hydrogen peroxide) and an “initiator” or“catalyst”. When present, bleaching agents will typically be at levelsof from about 1%, preferably from about 5% to about 30%, preferably toabout 20% by weight of the composition. If present, the amount of bleachactivator will typically be from about 0.1%, preferably from about 0.5%to about 60%, preferably to about 40% by weight, of the treatingcomposition comprising the bleaching agent-plus-bleach activator.

Bleaching Agents—Hydrogen peroxide sources are described in detail inthe herein incorporated Kirk Othmer's Encyclopedia of ChemicalTechnology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300“Bleaching Agents (Survey)”, and include the various forms of sodiumperborate and sodium percarbonate, including various coated and modifiedforms.

The preferred source of hydrogen peroxide used herein can be anyconvenient source, including hydrogen peroxide itself. For example,perborate, e.g., sodium perborate (any hydrate but preferably the mono-or tetra-hydrate), sodium carbonate peroxyhydrate or equivalentpercarbonate salts, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, or sodium peroxide can be used herein. Also useful aresources of available oxygen such as persulfate bleach (e.g., OXONE,manufactured by DuPont). Sodium perborate monohydrate and sodiumpercarbonate are particularly preferred. Mixtures of any convenienthydrogen peroxide sources can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with a silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

Compositions of the present invention may also comprise as the bleachingagent a chlorine-type bleaching material. Such agents are well known inthe art, and include for example sodium dichloroisocyanurate (“NaDCC”).However, chlorine-type bleaches are less preferred for compositionswhich comprise enzymes.

If peroxygen bleaching agents are used as all or part of the particulatematerial, they will generally comprise from about 0.1% to 30% by weightof the composition. More preferably, peroxygen bleaching agent willcomprise from about 1% to 20% by weight of the composition. Mostpreferably, peroxygen bleaching agent will be present to the extent offrom about 5% to 20% by weight of the composition.

(a) Bleach Activators—Preferably, the peroxygen bleach component in thecomposition is formulated with an activator (peracid precursor). Theactivator is present at levels of from about 0.01%, preferably fromabout 0.5%, more preferably from about 1%, most preferably from about 3%to about 20%, preferably to about 15%, more preferably to about 10%,most preferably to about 8%, by weight of the composition. Frequently,activators are employed such that the molar ratio of bleaching agent toactivator ranges from about 1:1 to 10:1, more preferably from about1.5:1 to 5:1. In addition, it has been found that bleach activators,when agglomerated with certain acids such as citric acid, are morechemically stable.

Preferred activators are selected from the group consisting oftetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C₁₀-OBS),benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (C₈-OBS),perhydrolyzable esters and mixtures thereof, most preferablybenzoylcaprolactam and benzoylvalerolactam. Particularly preferredbleach activators in the pH range from about 8 to about 9.5 are thoseselected having an OBS or VL leaving group.

Preferred hydrophobic bleach activators include, but are not limited to,nonanoyloxybenzenesulphonate (NOBS), 4-[N-nonaoyl)aminohexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS) an example ofwhich is described in U.S. Pat. No. 5,523,434,dodecanoyloxybenzenesulphonate (LOBS or C₁₂-OBS),10-undecenoyloxybenzenesulfonate (UDOBS or C₁₁-OBS with unsaturation inthe 10 position), and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those described in U.S. Pat. No.5,698,504 Christie et al., issued Dec. 16, 1997; U.S. Pat. No. 5,695,679Christie et al. issued Dec. 9, 1997; U.S. Pat. No. 5,686,401 Willey etal., issued Nov. 11, 1997; U.S. Pat. No. 5,686,014 Hartshorn et al.,issued Nov. 11, 1997; U.S. Pat. No. 5,405,412 Willey et al., issued Apr.11, 1995; U.S. Pat. No. 5,405,413 Willey et al., issued Apr. 11, 1995;U.S. Pat. No. 5,130,045 Mitchel et al., issued Jul. 14, 1992; and U.S.Pat. No. 4,412,934 Chung et al., issued Nov. 1, 1983, and copendingpatent applications U.S. Ser. Nos. 08/709,072, 08/064,564, all of whichare incorporated herein by reference.

The mole ratio of peroxygen bleaching compound (as AvO) to bleachactivator in the present invention generally ranges from at least 1:1,preferably from about 20:1, more preferably from about 10:1 to about1:1, preferably to about 3:1.

Quaternary substituted bleach activators may also be included. Thepresent cleaning compositions preferably comprise a quaternarysubstituted bleach activator (QSBA) or a quaternary substituted peracid(QSP); more preferably, the former. Preferred QSBA structures arefurther described in U.S. Pat. No. 5,686,015 Willey et al., issued Nov.11, 1997; U.S. Pat. No. 5,654,421 Taylor et al., issued Aug. 5, 1997;U.S. Pat. No. 5,460,747 Gosselink et al., issued Oct. 24, 1995; U.S.Pat. No. 5,584,888 Miracle et al., issued Dec. 17, 1996; and U.S. Pat.No. 5,578,136 Taylor et al., issued Nov. 26, 1996; all of which areincorporated herein by reference.

Highly preferred bleach activators useful herein are amide-substitutedas described in U.S. Pat. Nos. 5,698,504, 5,695,679, and 5,686,014 eachof which are cited herein above. Preferred examples of such bleachactivators include: (6-octanamidocaproyl) oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.

Other useful activators, disclosed in U.S. Pat. Nos. 5,698,504,5,695,679, 5,686,014 each of which is cited herein above and U.S. Pat.No. 4,966,723 Hodge et al., issued Oct. 30, 1990, includebenzoxazin-type activators, such as a C₆H₄ ring to which is fused in the1,2-positions a moiety —C(O)OC(R²)═N—.

Depending on the activator and precise application, good bleachingresults can be obtained from bleaching systems having with in-use pH offrom about 6 to about 13, preferably from about 9.0 to about 10.5.Typically, for example, activators with electron-withdrawing moietiesare used for near-neutral or sub-neutral pH ranges. Alkalis andbuffering agents can be used to secure such pH.

Acyl lactam activators, as described in U.S. Pat. Nos. 5,698,504,5,695,679 and 5,686,014, each of which is cited herein above, are veryuseful herein, especially the acyl caprolactams (see for example WO94-28102 A) and acyl valerolactams (see U.S. Pat. No. 5,503,639 Willeyet al., issued Apr. 2, 1996 incorporated herein by reference).

Cyclic imido bleach activators are represented by the formula:

wherein X is selected from substituted or unsubstituted, branched orlinear C₁-C₂₀ alkyl, substituted or unsubstituted, branched or linearC₂-C₂₀ alkylene. Preferably, X is branched or linear C₁-C₁₂ alkyl,branched or linear C₂-C₁₂ alkylene, more preferably branched or linearC₁-C₈ alkyl, branched or linear C₂-C₈ alkylene, most preferably linearC₁-C₆ alkyl. A is selected from:

and preferably is:

wherein n is selected from the numbers 0, 1, 2, 3 or 4. Preferably, n is0,1,2 or 3 and more preferably, 0,1, or 2. R¹ and R² are independentlyselected from the group consisting of hydrogen, chloride, bromide,iodide, substituted or unsubstituted branched or linear C₁-C₂₀ alkyl,substituted or unsubstituted branched or linear C₂-C₂₀ alkenyl,substituted or unsubstituted aryl, and substituted or unsubstitutedalkylaryl. Preferably R¹ and R² are independently hydrogen, chloride,substituted or unsubstituted branched or linear C₁-C₁₈ alkyl,substituted or unsubstituted branched or linear C₂-C₁₈ alkenyl,substituted or unsubstituted aryl, and substituted or unsubstitutedalkylaryl. More preferably, R¹ and R² are independently hydrogen,unsubstituted branched or linear C₁-C₁₆ alkyl, unsubstituted branched orlinear C₂-C₁₆ alkenyl, substituted or unsubstituted phenyl, substitutedor unsubstituted napthyl, substituted or unsubstituted alkylphenylsubstituted or unsubstituted alkylnapthyl. It is further preferred thatone of R¹ and R² is hydrogen or unsubstituted branched or linear C₁-C₆alkyl and the other is either an unsubstituted branched or linear C₁-C₁₆alkyl or an unsubstituted branched or linear C₂-C₁₆ alkenyl.

L is a modified or unmodified lactam leaving group. The lactams whichare suitable as leaving groups in the present application have thegeneric structure:

where R represents an optionally substituted alkenyl chain with at leasttwo carbon atoms in the alkenyl chain. This alkenyl chain forms a cyclicstructure with the —N— and —C(O)—. The term modified means that thealkenyl can be substituted at least once or that one or more of thealkenyl carbon atoms can be substituted by a suitable heterocycle or anycombination of both. Suitable heterocyclic chain substitutes are O, N,and S, with O being preferred. Suitable substituents include, but arenot limited to, C₁-C₆ alkyl, C₁-C₆ alkenyl, C₁-C₆ alkoxy, chloride,bromide, iodide. The preferred substituents are C₁-C₆ alkyl, C₁-C₆alkoxy and chloride. The most preferred modified lactam leaving groupsare: alpha-chlorocaprolactam, alpha-chlorovalerolactam,alpha,alpha-dichlorolactam, alpha,alpha-dichlorovalerolactam,alpha-methoxycaprolactam, alpha-methoxy-valerolactam,

and mixtures thereof.

When the lactams are unmodified, it means that they are contain nosubstituents other that hydrogen and have no heterocyclic substitutionof the alkenyl chain of R. R is preferably an alkenyl chain of two toseven carbon atoms. It is preferred that the lactam leaving group willbe unmodified. It is more preferred that the unsubstituted lactamleaving group will be either caprolactam or valerolactam. That is:

(b) Organic Peroxides, especially Diacyl Peroxides—These are extensivelyillustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol.17, John Wiley and Sons, 1982 at pages 27-90 and especially at pages63-72, all incorporated herein by reference. If a diacyl peroxide isused, it will preferably be one which exerts minimal adverse impact onspotting/filming.

(c) Metal-containing Bleach Catalysts—The present invention compositionsand methods may utilize metal-containing bleach catalysts that areeffective for use in bleaching compositions. Preferred are manganese andcobalt-containing bleach catalysts.

One type of metal-containing bleach catalyst is a catalyst systemcomprising a transition metal cation of defined bleach catalyticactivity, such as copper, iron, titanium, ruthenium tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243 Bragg, issued Feb. 2,1982.

Manganese Metal Complexes—If desired, the compositions herein can becatalyzed by means of a manganese compound. Such compounds and levels ofuse are well known in the art and include, for example, themanganese-based catalysts disclosed in U.S. Pat. Nos. 5,576,282;5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Pat. App.Pub. Nos. 549,271 A1, 549,272 A1, 544,440 A2, and 544,490 A1; Preferredexamples of these catalysts include Mn^(IV)₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂, Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂₋(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃,Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆), andmixtures thereof. Other metal-based bleach catalysts include thosedisclosed in U.S. Pat. Nos. 4,430,243 and 5,114,611. The use ofmanganese with various complex ligands to enhance bleaching is alsoreported in the following: U.S. Pat. Nos. 4,728,455; 5,284,944;5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

Cobalt Metal Complexes—Cobalt bleach catalysts useful herein are known,and are described, for example, in U.S. Pat. Nos. 5,597,936; 5,595,967;and 5,703,030; and M. L. Tobe, “Base Hydrolysis of Transition-MetalComplexes”, Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The mostpreferred cobalt catalyst useful herein are cobalt pentaamine acetatesalts having the formula [Co(NH₃)₅OAc] T_(y), wherein “OAc” representsan acetate moiety and “Ty” is an anion, and especially cobalt pentaamineacetate chloride, [Co(NH₃)₅OAc]Cl₂; as well as [Co(NH₃)₅OAc](OAc)₂;[Co(NH₃)₅OAc](PF₆)₂; [(Co(NH₃)₅OAc](SO₄); [Co -(NH₃)₅OAc](BF₄)₂; and[Co(NH₃)₅OAc](NO₃)₂ (herein “PAC”).

These cobalt catalysts are readily prepared by known procedures, such astaught for example in U.S. Pat. Nos. 5,597,936; 5,595,967; and5,703,030; in the Tobe article and the references cited therein; and inU.S. Pat. No. 4,810,410; J. Chem. Ed. (1989), 66 (12), 1043-45; TheSynthesis and Characterization of Inorganic Compounds, W. L. Jolly(Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979);Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979);Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56,22-25 (1952).

Transition Metal Complexes of Macropolycyclic Rigid Ligands—Compositionsherein may also suitably include as bleach catalyst a transition metalcomplex of a macropolycyclic rigid ligand. The phrase “macropolycyclicrigid ligand” is sometimes abbreviated as “MRL” in discussion below. Theamount used is a catalytically effective amount, suitably about 1 ppb ormore, for example up to about 99.9%, more typically about 0.001 ppm ormore, preferably from about 0.05 ppm to about 500 ppm (wherein “ppb”denotes parts per billion by weight and “ppm” denotes parts per millionby weight).

Suitable transition metals e.g., Mn are illustrated hereinafter.“Macropolycyclic” means a MRL is both a macrocycle and is polycyclic.“Polycyclic” means at least bicyclic. The term “rigid” as used hereinincludes “having a superstructure” and “cross-bridged”. “Rigid” has beendefined as the constrained converse of flexibility: see D. H. Busch.,Chemical Reviews., (1993), 93, 847-860, incorporated by reference. Moreparticularly, “rigid” as used herein means that the MRL must bedeterminably more rigid than a macrocycle (“parent macrocycle”) which isotherwise identical (having the same ring size and type and number ofatoms in the main ring) but lacking a superstructure (especially linkingmoieties or, preferably cross-bridging moieties) found in the MRL's. Indetermining the comparative rigidity of macrocycles with and withoutsuperstructures, the practitioner will use the free form (not themetal-bound form) of the macrocycles. Rigidity is well-known to beuseful in comparing macrocycles; suitable tools for determining,measuring or comparing rigidity include computational methods (see, forexample, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancocket al., Inorganica Chimica Acta, (1989), 164, 73-84.

Preferred MRL's herein are a special type of ultra-rigid ligand which iscross-bridged. A “cross-bridge” is nonlimitingly illustrated in 1.11hereinbelow. In 1.11, the cross-bridge is a—CH₂CH₂— moiety. It bridgesN¹ and N⁸ in the illustrative structure. By comparison, a “same-side”bridge, for example if one were to be introduced across N¹ and N¹² in1.11, would not be sufficient to constitute a “cross-bridge” andaccordingly would not be preferred.

Suitable metals in the rigid ligand complexes include Mn(II), Mn(III),Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I),Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V),Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI),Pd(II), Ru(II), Ru(III), and Ru(IV). Preferred transition-metals in theinstant transition-metal bleach catalyst include manganese, iron andchromium.

More generally, the MRL's (and the corresponding transition-metalcatalysts) herein suitably comprise:

(a) at least one macrocycle main ring comprising four or moreheteroatoms; and

(b) a covalently connected non-metal superstructure capable ofincreasing the rigidity of the macrocycle, preferably selected from

(i) a bridging superstructure, such as a linking moiety;

(ii) a cross-bridging superstructure, such as a cross-bridging linkingmoiety; and

(iii) combinations thereof.

The term “superstructure” is used herein as defined in the literature byBusch et al., see, for example, articles by Busch in “Chemical Reviews”.

Preferred superstructures herein not only enhance the rigidity of theparent macrocycle, but also favor folding of the macrocycle so that itco-ordinates to a metal in a cleft. Suitable superstructures can beremarkably simple, for example a linking moiety such as any of thoseillustrated in FIG. 1 and FIG. 2 below, can be used.

wherein n is an integer, for example from 2 to 8, preferably less than6, typically 2 to 4, or

wherein m and n are integers from about 1 to 8, more preferably from 1to 3; Z is N or CH; and T is a compatible substituent, for example H,alkyl, trialkylammonium, halogen, nitro, sulfonate, or the like. Thearomatic ring in 1.10 can be replaced by a saturated ring, in which theatom in Z connecting into the ring can contain N, O, S or C.

Suitable MRL's are further nonlimitingly illustrated by the followingcompound:

This is a MRL in accordance with the invention which is a highlypreferred, cross-bridged, methyl-substituted (all nitrogen atomstertiary) derivative of cyclam. Formally, this ligand is named5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane using theextended von Baeyer system. See “A Guide to IUPAC Nomenclature ofOrganic Compounds: Recommendations 1993”, R. Panico, W. H. Powell andJ-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; seeespecially section R-2.4.2.1.

Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which aresuitable for use in the invention compositions can in general includeknown compounds where they conform with the definition herein, as wellas, more preferably, any of a large number of novel compounds expresslydesigned for the present laundry or cleaning uses, and non-limitinglyillustrated by any of the following:

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Hexafluorophosphate

Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Hexafluorophosphate

Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Tetrafluoroborate

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Hexafluorophosphate

Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II).

As a practical matter, and not by way of limitation, the compositionsand cleaning processes herein can be adjusted to provide on the order ofat least one part per hundred million of the active bleach catalystspecies in the aqueous washing medium, and will preferably provide fromabout 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm toabout 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, ofthe bleach catalyst species in the wash liquor. In order to obtain suchlevels in the wash liquor of an automatic washing process, typicalcompositions herein will comprise from about 0.0005% to about 0.2%, morepreferably from about 0.004% to about 0.08%, of bleach catalyst,especially manganese or cobalt catalysts, by weight of the bleachingcompositions.

(d) Other Bleach Catalysts—The compositions herein may comprise one ormore other bleach catalysts. Preferred bleach catalysts are zwitterionicbleach catalysts, which are described in U.S. Pat. No. 5,576,282(especially 3-(3,4-dihydroisoquinolinium) propane sulfonate. Otherbleach catalysts include cationic bleach catalysts are described in U.S.Pat. Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515,5,550,256, and WO 95/13351, WO 95/13352, and WO 95/13353.

As a practical matter, and not by way of limitation, the compositionsand cleaning processes herein can be adjusted to provide on the order ofat least one part per hundred million of the active bleach catalystspecies in the aqueous washing medium, and will preferably provide fromabout 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm toabout 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, ofthe bleach catalyst species in the wash liquor. In order to obtain suchlevels in the wash liquor of an automatic washing process, typicalcompositions herein will comprise from about 0.0005% to about 0.2%, morepreferably from about 0.004% to about 0.08%, of bleach catalyst,especially manganese or cobalt catalysts, by weight of the cleaningcompositions.

(e) Preformed peracids—Also suitable as bleaching agents are preformedperacids, such as phthalimido-peroxy-caproic acid (“PAP”). See forexample U.S. Pat. Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757 and5,132,431.

Enzymes—The treating compositions herein may also optionally contain oneor more types of detergent enzymes. Such enzymes can include otherproteases, amylases and lipases. They may be incorporated into thenon-aqueous liquid detergent compositions herein in the form ofsuspensions, “marumes” or “prills”. Another suitable type of enzymecomprises those in the form of slurries of enzymes in nonionicsurfactants, e.g., the enzymes marketed by Novo Nordisk under thetradename “SL” or the microencapsulated enzymes marketed by Novo Nordiskunder the tradename “LDP.” Suitable enzymes and levels of use aredescribed in U.S. Pat. Nos. 5,576,282, 5,705,464 and 5,710,115.

Enzymes added to the compositions herein in the form of conventionalenzyme prills are especially preferred for use herein. Such prills willgenerally range in size from about 100 to 1,000 microns, more preferablyfrom about 200 to 800 microns and will be suspended throughout thenon-aqueous liquid phase of the composition. Prills in the compositionsof the present invention have been found, in comparison with otherenzyme forms, to exhibit especially desirable enzyme stability in termsof retention of enzymatic activity over time. Thus, compositions whichutilize enzyme prills need not contain conventional enzyme stabilizingsuch as must frequently be used when enzymes are incorporated intoaqueous liquid detergents.

However, enzymes added to the compositions herein may be in the form ofgranulates, preferably T-granulates.

“Detersive enzyme”, as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a laundry, hard surfacecleaning or personal care detergent composition. Preferred detersiveenzymes are hydrolases such as proteases, amylases and lipases.Preferred enzymes for laundry purposes include, but are not limited to,proteases, cellulases, lipases and peroxidases. Highly preferred forautomatic dishwashing are amylases and/or proteases, including bothcurrent commercially available types and improved types which, thoughmore and more bleach compatible though successive improvements, have aremaining degree of bleach deactivation susceptibility.

Examples of suitable enzymes include, but are not limited to,hemicellulases, peroxidases, proteases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, keratanases,reductases, oxidases, phenoloxidases, lipoxygenases, ligninases,pullulanases, tannases, pentosanases, malanases, glucanases,arabinosidases, hyaluronidase, chondroitinase, laccase, mannanases,xyloglucanases and known amylases, or mixtures thereof.

Examples of such suitable enzymes are disclosed in U.S. Pat. Nos.5,705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950.

Peroxidase enzymes are used in combination with oxygen sources, e.g.percarbonate, perborate, persulfate, hydrogen peroxide, etc and with aphenolic substrate as bleach enhancing molecule. They are used for“solution bleaching”, i.e. to prevent transfer of dyes or pigmentsremoved from substrates during wash operations to other substrates inthe wash solution. Peroxidase enzymes are known in the art, and include,for example, horseradish peroxidase, ligninase and haloperoxidase suchas chloro- and bromo-peroxidase. Suitable peroxidases andperoxidase-containing detergent compositions are disclosed, for example,in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,576,282, 5,728,671 and5,707,950, PCT International Application WO 89/099813, WO89/09813 and inEuropean Patent application EP No. 91202882.6, filed on Nov. 6, 1991 andEP No. 96870013.8, filed Feb. 20, 1996. Also suitable is the laccaseenzyme.

Enhancers are generally comprised at a level of from 0.1% to 5% byweight of total composition. Preferred enhancers are substitutedphenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT),10-ethylphenothiazine4carboxylic acid (EPC), 10-phenoxazinepropionicacid (POP) and 10-methylphenoxazine (described in WO 94/12621) andsubstitued syringates (C3-C5 substitued alkyl syringates) and phenols.Sodium percarbonate or perborate are preferred sources of hydrogenperoxide. Said peroxidases are normally incorporated in the cleaningcomposition at levels from 0.0001% to 2% of pure enzyme by weight of thecleaning composition.

Enzymatic systems may be used as bleaching agents. The hydrogen peroxidemay also be present by adding an enzymatic system (i.e. an enzyme and asubstrate therefore) which is capable of generating hydrogen peroxide atthe beginning or during the washing and/or rinsing process. Suchenzymatic systems are disclosed in EP Patent Application 91202655.6filed Oct. 9, 1991.

Other preferred enzymes that can be included in the cleaningcompositions of the present invention include lipases. Suitable lipaseenzymes for detergent usage include those produced by microorganisms ofthe Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, asdisclosed in British Patent No. 1,372,034. Suitable lipases includethose which show a positive immunological cross-reaction with theantibody of the lipase, produced by the microorganism Pseudomonasfluorescent IAM 1057. This lipase is available from Amano PharmaceuticalCo. Ltd., Nagoya, Japan, under the trade name Lipase P “Amano,”hereinafter referred to as “Amano-P”. Other suitable commercial lipasesinclude Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacterviscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. andDisoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.Especially suitable lipases are lipases such as M1 Lipase^(R) andLipomax^(R) (Gist-Brocades) and Lipolase^(R) and LipolaseUltra^(R)(Novo) which have found to be very effective when used incombination with the compositions of the present invention. Alsosuitable are the lipolytic enzymes described in EP 258 068, WO 92/05249and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO96/00292 by Unilever.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as aspecial kind of lipase, namely lipases which do not require interfacialactivation. Addition of cutinases to cleaning compositions have beendescribed in e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant GeneticSystem) and WO 94/14963 and WO 94/14964 (Unilever).

Lipases and/or cutinases, when present, are normally incorporated in thecleaning composition at levels from 0.0001% to 2% of pure enzyme byweight of the cleaning composition.

In addition to the above referenced lipases, phospholipases may beincorporated into the cleaning compositions of the present invention.Nonlimiting examples of suitable phospholipases included: EC 3.1.1.32Phospholipase A1; EC 3.1.1.4 Phospholipase A2; EC 3.1.1.5 Lysopholipase;EC 3.1.4.3 Phospholipase C; EC 3.1.4.4. Phospolipase D. Commerciallyavailable phospholipases include LECITASE® from Novo Nordisk A/S ofDenmark and Phospholipase A2 from Sigma. When phospolipases are includedin the compositions of the present invention, it is preferred thatamylases are also included. Without desiring to be bound by theory, itis believed that the combined action of the phospholipase and amylaseprovide substantive stain removal, especially on greasy/oily, starchyand highly colored stains and soils. Preferably, the phospholipase andamylase, when present, are incorporated into the compositions of thepresent invention at a pure enzyme weight ratio between 4500:1 and 1:5,more preferably between 50:1 and 1:1.

Suitable proteases are the subtilisins which are obtained fromparticular strains of B. subtilis and B. licheniformis (subtilisin BPNand BPN′). One suitable protease is obtained from a strain of Bacillus,having maximum activity throughout the pH range of 8-12, developed andsold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter “Novo”.The preparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Proteolytic enzymes also encompass modified bacterialserine proteases, such as those described in European Patent ApplicationSerial Number 87 303761.8, filed Apr. 28, 1987 (particularly pages 17,24 and 98), and which is called herein “Protease B”, and in EuropeanPatent Application 199,404, Venegas, published Oct. 29, 1986, whichrefers to a modified bacterial serine protealytic enzyme which is called“Protease A” herein. Suitable is the protease called herein “ProteaseC”, which is a variant of an alkaline serine protease from Bacillus inwhich Lysine replaced arginine at position 27, tyrosine replaced valineat position 104, serine replaced asparagine at position 123, and alaninereplaced threonine at position 274. Protease C is described in EP90915958:4, corresponding to WO 91/06637, Published May 16, 1991.Genetically modified variants, particularly of Protease C, are alsoincluded herein.

A preferred protease referred to as “Protease D” is a carbonyl hydrolaseas described in U.S. Pat. No. 5,677,272, and WO95/10591. Also suitableis a carbonyl hydrolase variant of the protease described in WO95/10591,having an amino acid sequence derived by replacement of a plurality ofamino acid residues replaced in the precursor enzyme corresponding toposition +210 in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130,+132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218,and +222, where the numbered position corresponds to naturally-occurringsubtilisin from Bacillus amyloliquefaciens or to equivalent amino acidresidues in other carbonyl hydrolases or subtilisins, such as Bacilluslentus subtilisin (co-pending patent application U.S. Serial No.60/048,550, filed Jun. 4, 1997 and PCT International Application SerialNo. PCT/IB98/00853).

Also suitable for the present invention are proteases described inpatent applications EP 251 446 and WO 91/06637, protease BLAP® describedin WO91/02792 and their variants described in WO 95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338 described inWO 93/18140 A to Novo. Enzymatic detergents comprising protease, one ormore other enzymes, and a reversible protease inhibitor are described inWO 92/03529 A to Novo. When desired, a protease having decreasedadsorption and increased hydrolysis is available as described in WO95/07791 to Procter & Gamble. A recombinant trypsin-like protease fordetergents suitable herein is described in WO 94/25583 to Novo. Othersuitable proteases are described in EP 516 200 by Unilever.

Particularly useful proteases are described in PCT publications: WO95/30010; WO 95/30011; and WO 95/29979. Suitable proteases arecommercially available as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®,EVERLASE® and KANNASE® all from Novo Nordisk A/S of Denmark, and asMAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from GenencorInternational (formerly Gist-Brocades of The Netherlands).

Other particularly useful proteases are multiply-substituted proteasevariants comprising a substitution of an amino acid residue with anothernaturally occurring amino acid residue at an amino acid residue positioncorresponding to position 103 of Bacillus amyloliquefaciens subtilisinin combination with a substitution of an amino acid residue with anothernaturally occurring amino acid residue at one or more amino acid residuepositions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17,18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62,68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106,107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133,134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167, 170, 173,174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205,206, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227,228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248,249, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263,265, 268, 269, 270, 271, 272, 274 and 275 of Bacillus amyloliquefacienssubtilisin; wherein when said protease variant includes a substitutionof amino acid residues at positions corresponding to positions 103 and76, there is also a substitution of an amino acid residue at one or moreamino acid residue positions other than amino acid residue positionscorresponding to positions 27, 99, 101, 104, 107, 109, 123, 128, 166,204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillusamyloliquefaciens subtilisin and/or multiply-substituted proteasevariants comprising a substitution of an amino acid residue with anothernaturally occurring amino acid residue at one or more amino acid residuepositions corresponding to positions 62, 212, 230, 232, 252 and 257 ofBacillus amyloliquefaciens subtilisin as described in PCT ApplicationNos. PCT/US98/22588, PCT/US98/22482 and PCT/US98/22486 all filed on Oct.23, 1998 from The Procter & Gamble Company (P&G Cases 7280&, 7281& and7282L, respectively). More preferably the protease variant includes asubstitution set selected from the group consisting of:

12/76/103/104/130/222/245/261;

62/103/104/159/232/236/245/248/252;

62/103/104/159/213/232/236/245/248/252;

62/101/103/104/159/212/213/232/236/245/248/252;

68/103/104/159/232/236/245;

68/103/104/159/230/232/236/245;

68/103/104/159/209/232/236/245;

68/103/104/159/232/236/245/257;

68/76/103/104/159/213/232/236/245/260;

68/103/104/159/213/232/236/245/248/252;

68/103/104/159/183/232/236/245/248/252;

68/103/104/159/185/232/236/245/248/252;

68/103/104/159/185/210/232/2361245/248/252;

68/103/104/159/210/232/236/245/248/252;

68/103/104/159/213/232/236/245;

98/103/104/159/232/236/245/248/252;

98/102/103/104/159/212/232/236/245/248/252;

103/104/159/232/236/245/248/252;

102/103/104/1 59/232/236/245/248/252;

103/104/159/230/236/245;

103/104/159/232/236/245/248/252;

103/104/159/217/232/236/245/248/252;

103/104/130/159/232/236/245/248/252;

103/104/131/159/232/236/245/248/252;

103/104/159/213/232/236/245/248/252; and

103/104/159/232/236/245.

Still even more preferably the protease variant includes a substitutionset selected from the group consisting of:

12R/76D/103A/104T/130T/222S/245R/261D;

62D/103A/104I/159D/232V/236H/245R/248D/252K;

62D/103A/104I/159D/213R/232V/236H/245R/248D/252K;

68A/103A/104I/159D/209W/232V/236H/245R;

68A/76D/103A/104I/159D/213R/232V/236H/245R/260A;

68A/103A/104I/159D/213E/232V/236H/245R/248D/252K;

68A/103A/104I/159D/183D/232V/236H/245R/248D/252K;

68A/103A/104I/159D/232V/236H/245R;

68A/103A/104I/159D/230V/232V/236H/245R;

68A/103A/104I/159D/232V/236H/245R/257V;

68A/103A/104I/159D/213G/232V/236H/245R/248D/252K;

68A/103A/104I/159D/185D/232V/236H/245R/248D/252K;

68A/103A/104I/159D/185D/210L/232V/236H/245R/248D/252K;

68A/103A/104I/159D/210L/232V/236H/245R/248D/252K;

68A/103A/104I/159D/213G/232V/236H/245R;

98L/103A/104I/159D/232V/236H/245R/248D/252K;

98L/102A/103A/104I/159D/212G/232V/236H/245R/248D/252K;

101G/103A/104I/159D/232V/236H/245R/248D/252K;

102A/103A/104I/159D/232V/236H/245R/248D/252K;

103A/104I/159D/230V/236H/245R;

103A/104I/159D/232V/236H/245R/248D/252K;

103A/104I/159D/217E/232V/236H/245R/248D/252K;

103A/104I/130G/159D/232V/236H/245R/248D/252K;

103A/104I/131 V/159D/232V/236H/245R/248D/252K;

103A/104I/159D/213R/232V/236H/245R/248D/252K.

Such amylolytic enzymes, when present, are incorporated in the cleaningcompositions of the present invention a level of from 0.0001% to 2%,preferably from 0.00018% to 0.06%, more preferably from 0.00024% to0.048% pure enzyme by weight of the composition.

The compositions of the present invention may also comprise a mannanaseenzyme. Preferably, the mannanase is selected from the group consistingof: three mannans-degrading enzymes: EC 3.2.1.25: β-mannosidase, EC3.2.1.78: Endo-1,4-β-mannosidase, referred therein after as “mannanase”and EC 3.2.1.100: 1,4-β-mannobiosidase and mixtures thereof (IUPACClassification—Enzyme nomenclature, 1992 ISBN 0-12-227165-3 AcademicPress).

More preferably, the treating compositions of the present invention,when a mannanase is present, comprise a β-1,4-Mannosidase (E.C.3.2.1.78) referred to as Mannanase. The term “mannanase” or“galactomannanase” denotes a mannanase enzyme defined according to theart as officially being named mannan endo-1,4-beta-mannosidase andhaving the alternative names beta-mannanase and endo-1,4-mannanase andcatalyzing the reaction: random hydrolysis of 1,4-beta-D-mannosidiclinkages in mannans, galactomannans, glucomannans, andgalactoglucomannans.

In particular, Mannanases (EC 3.2.1.78) constitute a group ofpolysaccharases which degrade mannans and denote enzymes which arecapable of cleaving polyose chains containing mannose units, i.e. arecapable of cleaving glycosidic bonds in mannans, glucomannans,galactomannans and galactogluco-mannans. Mannans are polysaccharideshaving a backbone composed of β-1,4-linked mannose; glucomannans arepolysaccharides having a backbone or more or less regularly alternatingβ-1,4 linked mannose and glucose; galactomannans and galactoglucomannansare mannans and glucomannans with α-1,6 linked galactose sidebranches.These compounds may be acetylated.

The degradation of galactomannans and galactoglucomannans is facilitatedby full or partial removal of the galactose sidebranches. Further thedegradation of the acetylated mannans, glucomannans, galactomannans andgalactogluco-mannans is facilitated by full or partial deacetylation.Acetyl groups can be removed by alkali or by mannan acetylesterases. Theoligomers which are released from the mannanases or by a combination ofmannanases and α-galactosidase and/or mannan acetyl esterases can befurther degraded to release free maltose by β-mannosidase and/orβ-glucosidase.

Mannanases have been identified in several Bacillus organisms. Forexample, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 11, pp.3505-3510 (1990) describes a beta-mannanase derived from Bacillusstearothermophilus in dimer form having molecular weight of 162 kDa andan optimum pH of 5.5-7.5. Mendoza et al., World J. Microbiol. Biotech.,Vol. 10, No. 5, pp. 551-555 (1994) describes a beta-mannanase derivedfrom Bacillus subtilis having a molecular weight of 38 kDa, an optimumactivity at pH 5.0 and 55C and a pI of 4.8. JP-03047076 discloses abeta-mannanase derived from Bacillus sp., having a molecular weight of373 kDa measured by gel filtration, an optimum pH of 8-10 and a pI of5.3-5.4. JP-63056289 describes the production of an alkaline,thermostable beta-mannanase which hydrolyses beta-1,4-D-mannopyranosidebonds of e.g. mannans and produces manno-oligosaccharides. JP-63036774relates to the Bacillus microorganism FERM P-8856 which producesbeta-mannanase and beta-mannosidase at an alkaline pH. JP-08051975discloses alkaline beta-mannanases from alkalophilic Bacillus sp.AM-001. A purified mannanase from Bacillus amyloliquefaciens useful inthe bleaching of pulp and paper and a method of preparation thereof isdisclosed in WO 97/11164. WO 91/18974 describes a hemicellulase such asa glucanase, xylanase or mannanase active at an extreme pH andtemperature. WO 94/25576 discloses an enzyme from Aspergillus aculeatus,CBS 101.43, exhibiting mannanase activity which may be useful fordegradation or modification of plant or algae cell wall material. WO93/24622 discloses a mannanase isolated from Trichoderma reseei usefulfor bleaching lignocellulosic pulps. An hemicellulase capable ofdegrading mannan-containing hemicellulose is described in WO91/18974 anda purified mannase from Bacillus amyloliquefaciens is described inWO97/11164.

Preferably, the mannanase enzyme will be an alkaline mannanase asdefined below, more preferably, a mannanase originating from a bacterialsource. Especially, the laundry detergent composition of the presentinvention will comprise an alkaline mannanase selected from themannanase from the strain Bacillus agaradhaerens NICMB 40482; themannanase from Bacillus subtilis strain 168, gene yght; the mannanasefrom Bacillus sp. I633 and/or the mannanase from Bacillus sp. AAI12.Most preferred mannanase for the inclusion in the detergent compositionsof the present invention is the mannanase enzyme originating fromBacillus sp. I633 as described in the co-pending Danish patentapplication No. PA 1998 01340.

The terms “alkaline mannanase enzyme” is meant to encompass an enzymehaving an enzymatic activity of at least 10%, preferably at least 25%,more preferably at least 40% of its maximum activity at a given pHranging from 7 to 12, preferably 7.5 to 10.5.

The alkaline mannanase from Bacillus agaradhaerens NICMB 40482 isdescribed in the co-pending U.S. patent application Ser. No. 09/111,256.More specifically, this mannanase is:

i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or

ii) a polypeptide comprising an amino acid sequence as shown inpositions 32-343 of SEQ ID NO:2 as shown in U.S. patent application Ser.No. 09/111,256; or

iii) an analogue of the polypeptide defined in i) or ii) which is atleast 70% homologous with said polypeptide, or is derived from saidpolypeptide by substitution, deletion or addition of one or severalamino acids, or is immunologically reactive with a polyclonal antibodyraised against said polypeptide in purified form.

Also encompassed is the corresponding isolated polypeptide havingmannanase activity selected from the group consisting of:

(a) polynucleotide molecules encoding a polypeptide having mannanaseactivity and comprising a sequence of nucleotides as shown in SEQ ID NO:1 from nucleotide 97 to nucleotide 1029 as shown in U.S. patentapplication Ser. No. 09/111,256;

(b) species homologs of (a);

(c) polynucleotide molecules that encode a polypeptide having mannaseactivity that is at least 70% identical to the amino acid sequence ofSEQ ID NO: 2 from amino acid residue 32 to amino acid residue 343 asshown in U.S. patent application Ser. No. 09/111,256;

(d) molecules complementary to (a), (b) or (c); and

(e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The plasmid pSJ1678 comprising the polynucleotide molecule (the DNAsequence) encoding said mannanase has been transformed into a strain ofthe Escherichia coli which was deposited by the inventors according tothe Budapest Treaty on the International Recognition of the Deposit ofMicroorganisms for the Purposes of Patent Procedure at the DeutscheSammlung von Milroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b,D-38124 Braunschweig, Federal Republic of Germany, on May 18, 1998 underthe deposition number DSM 12180.

A second more preferred enzyme is the mannanase from the Bacillussubtilis strain 168, which is described in the co-pending U.S. patentapplication Ser. No. 09/095,163. More specifically, this mannanase is:

i) is encoded by the coding part of the DNA sequence shown in SEQ ID No.5 shown in the U.S. patent application Ser. No. 09/095,163 or ananalogue of said sequence; and/or

ii) a polypeptide comprising an amino acid sequence as shown SEQ ID NO:6shown in the U.S. patent application Ser. No. 09/095,163; or

iii) an analogue of the polypeptide defined in ii) which is at least 70%homologous with said polypeptide, or is derived from said polypeptide bysubstitution, deletion or addition of one or several amino acids, or isimmunologically reactive with a polyclonal antibody raised against saidpolypeptide in purified form.

Also encompassed in the corresponding isolated polypeptide havingmannanase activity selected from the group consisting of:

(a) polynucleotide molecules encoding a polypeptide having mannanaseactivity and comprising a sequence of nucleotides as shown in SEQ IDNO:5 as shown in the U.S. patent application Ser. No. 09/095,163

(b) species homologs of (a);

(c) polynucleotide molecules that encode a polypeptide having mannanaseactivity that is at least 70% identical to the amino acid sequence ofSEQ ID NO: 6 as shown in the U.S. patent application Ser. No.09/095,163;

(d) molecules complementary to (a), (b) or (c); and

(e) degenerate nucleotide sequences of (a), (b), (c) or (d).

A third more preferred mannanase is described in the co-pending Danishpatent application No. PA 1998 01340. More specifically, this mannanaseis:

i) a polypeptide produced by Bacillus sp. 1633;

ii) a polypeptide comprising an amino acid sequence as shown inpositions 33-340 of SEQ ID NO:2 as shown in the Danish application No.PA 1998 01340; or

iii) an analogue of the polypeptide defined in i) or ii) which is atleast 65% homologous with said polypeptide, is derived from saidpolypeptide by substitution, deletion or addition of one or severalamino acids, or is immunologically reactive with a polyclonal antibodyraised against said polypeptide in purified form.

Also encompassed is the corresponding isolated polynucleotide moleculeselected from the group consisting of:

(a) polynucleotide molecules encoding a polypeptide having mannanaseactivity and comprising a sequence of nucleotides as shown in SEQ ID NO:1 from nucleotide 317 to nucleotide 1243 the Danish application No. PA1998 01340;

(b) species homologs of (a);

(c) polynucleotide molecules that encode a polypeptide having mannanaseactivity that is at least 65% identical to the amino acid sequence ofSEQ ID NO: 2 from amino acid residue 33 to amino acid residue 340 theDanish application No. PA 1998 01340;

(d) molecules complementary to (a), (b) or (c); and

(e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The plasmid pBXM3 comprising the polynucleotide molecule (the DNAsequence) encoding a mannanase of the present invention has beentransformed into a strain of the Escherichia coli which was deposited bythe inventors according to the Budapest Treaty on the InternationalRecognition of the Deposit of Microorganisms for the Purposes of PatentProcedure at the Deutsche Sammlung von Mikroorganismen und ZellkulturenGmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic ofGermany, on May 29, 1998 under the deposition number DSM 12197.

A fourth more preferred mannanase is described in the Danish co-pendingpatent application No. PA 1998 01341. More specifically, this mannanaseis:

i) a polypeptide produced by Bacillus sp. AAI 12;

ii) a polypeptide comprising an amino acid sequence as shown inpositions 25-362 of SEQ ID NO:2 as shown in the Danish application No.PA 1998 01341; or

iii) an analogue of the polypeptide defined in i) or ii) which is atleast 65% homologous with said polypeptide, is derived from saidpolypeptide by substitution, deletion or addition of one or severalamino acids, or is immunologically reactive with a polyclonal antibodyraised against said polypeptide in purified form.

Also encompassed is the corresponding isolated polynucleotide moleculeselected from the group consisting of

(a) polynucleotide molecules encoding a polypeptide having mannanaseactivity and comprising a sequence of nucleotides as shown in SEQ ID NO:1 from nucleotide 225 to nucleotide 1236 as shown in the Danishapplication No. PA 1998 01341;

(b) species homologs of (a);

(c) polynucleotide molecules that encode a polypeptide having mannanaseactivity that is at least 65% identical to the amino acid sequence ofSEQ ID NO: 2 from amino acid residue 25 to amino acid residue 362 asshown in the Danish application No. PA 1998 01341;

(d) molecules complementary to (a), (b) or (c); and

(e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The plasmid pBXM1 comprising the polynucleotide molecule (the DNAsequence) encoding a mannanase of the present invention has beentransformed into a strain of the Escherichia coli which was deposited bythe inventors according to the Budapest Treaty on the InternationalRecognition of the Deposit of Microorganisms for the Purposes of PatentProcedure at the Deutsche Sammlung von Mikroorganismen und ZellkulturenGmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic ofGermany, on Oct. 7, 1998 under the deposition number DSM 12433.

The mannanase, when present, is incorporated into the treatingcompositions of the present invention preferably at a level of from0.0001% to 2%, more preferably from 0.0005% to 0.1%, most preferred from0.001% to 0.02% pure enzyme by weight of the composition.

The compositions of the present invention may also comprise axyloglucanase enzyme. Suitable xyloglucanases for the purpose of thepresent invention are enzymes exhibiting endoglucanase activity specificfor xyloglucan, preferably at a level of from about 0.001% to about 1%,more preferably from about 0.01% to about 0.5%, by weight of thecomposition. As used herein, the term “endoglucanase activity” means thecapability of the enzyme to hydrolyze 1,4-β-D-glycosidic linkagespresent in any cellulosic material, such as cellulose, cellulosederivatives, lichenin, β-D-glucan, or xyloglucan. The endoglucanaseactivity may be determined in accordance with methods known in the art,examples of which are described in WO 94/14953 and hereinafter. One unitof endoglucanase activity (e.g. CMCU, AVIU, XGU or BGU) is defined asthe production of 1 μmol reducing sugar/min from a glucan substrate, theglucan substrate being, e.g., CMC (CMCU), acid swollen Avicell (AVIU),xyloglucan (XGU) or cereal β-glucan (BGU). The reducing sugars aredetermined as described in WO 94/14953 and hereinafter. The specificactivity of an endoglucanase towards a substrate is defined as units/mgof protein.

Suitable are enzymes exhibiting as its highest activity XGUendoglucanase activity (hereinafter “specific for xyloglucan”), whichenzyme:

i) is encoded by a DNA sequence comprising or included in at least oneof the following partial sequences

(a) ATTCATTTGT GGACAGTGGA C (SEQ ID No: 1)

(b) GTTGATCGCA CATTGAACCA (SEQ ID NO: 2)

(c) ACCCCAGCCG ACCGATTGTC (SEQ ID NO: 3)

(d) CTTCCTTACC TCACCATCAT (SEQ ID NO: 4)

(e) TTAACATCTT TTCACCATGA (SEQ ID NO: 5)

(f) AGCTTTCCCT TCTCTCCCTT (SEQ ID NO: 6)

(g) GCCACCCTGG CTTCCGCTGC CAGCCTCC (SEQ ID NO: 7)

(h) GACAGTAGCA ATCCAGCATT (SEQ ID NO: 8)

(i) AGCATCAGCC GCTTTGTACA (SEQ ID NO: 9)

(j) CCATGAAGTT CACCGTATTG (SEQ ID NO: 10)

(k) GCACTGCTTC TCTCCCAGGT (SEQ ID NO: 11)

(l) GTGGGCGGCC CCTCAGGCAA (SEQ ID NO: 12)

(m) ACGCTCCTCC AATTTTCTCT (SEQ ID NO: 13)

(n) GGCTGGTAG TAATGAGTCT (SEQ ID NO: 14)

(o) GGCGCAGAGT TTGGCCAGGC (SEQ ID NO: 15)

(p) CAACATCCCC GGTGTTCTGG G (SEQ ID NO: 16)

(q) AAAGATTCAT TTGTGGACAG TGGACGTRGA TCGCACATTG AACCAACCCC AGCCGACCGATTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTTTCAC CATGAAGCTT TCCCTTCTCTCCCTTGCCAC CCTGGCTTCC GCTGCCAGCC TCCAGCGCCG CACACTTCTG CGGTCAGTGGGATACCGCCA CCGCCGGTGA CTCACCCTG TACAACGACC TTTGGGGCGA GACGGCCGGCACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACCATCGC TTGTCACACCAGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GCCAACG (SEQ ID NO:17) or

(r) CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTG CGTGGCGGAGGCTGCCGGGA GACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCG TGTTTCAGTCCCTAGGCAGG ATACCGGAAA ACCGTGTGGT AGGAGGTTTA TAGGTTTCCA GGAGACGCTGTATAGGGGAT AAATGAGATT GAATGGTGGC CACACTCAAA CCAACCAGGT CCTGTACATACAATGCATAT ACCAATTATA CCTACCAAAA AAAAAAAAAA AAAAAAAAAA AAAA (SEQ IDNO:18)

or a sequence homologous thereto encoding a polypeptide specific forxyloglucan with endoglucanase activity,

ii) is immunologically reactive with an antibody raised against a highlypurified endoglucanase encoded by the DNA sequence defined in i) andderived from Aspergillus aculeatus, CBS 101.43, and is specific forxyloglucan.

More specifically, as used herein the term “specific for xyloglucan”means that the endoglucanase enzyme exhibits its highest endoglucanaseactivity on a xyloglucan substrate, and preferably less than 75%activity, more preferably less than 50% activity, most preferably lessthan about 25% activity, on other cellulose-containing substrates suchas carboxymethyl cellulose, cellulose, or other glucans.

Preferably, the specificity of an endoglucanase towards xyloglucan isfurther defined as a relative activity determined as the release ofreducing sugars at optimal conditions obtained by incubation of theenzyme with xyloglucan and the other substrate to be tested,respectively. For instance, the specificity may be defined as thexyloglucan to β-glucan activity (XGU/BGU), xyloglucan to carboxy methylcellulose activity (XGU/CMCU), or xyloglucan to acid swollen Avicellactivity (XGU/AVIU), which is preferably greater than about 50, such as75, 90 or 100.

The term “derived from” as used herein refers not only to anendoglucanase produced by strain CBS 101.43, but also an endoglucanaseencoded by a DNA sequence isolated from strain CBS 101.43 and producedin a host organism transformed with said DNA sequence. The term“homologue” as used herein indicates a polypeptide encoded by DNA whichhybridizes to the same probe as the DNA coding for an endoglucanaseenzyme specific for xyloglucan under certain specified conditions (suchas presoaking in 5×SSC and prehybridizing for 1 h at −40° C. in asolution of 5×SSC, 5×Denhardt's solution, and 50 μg of denaturedsonicated calf thymus DNA, followed by hybridization in the samesolution supplemented with 50 μCi 32-P-dCTP labelled probe for 18 h at−40° C. and washing three times in 2×SSC, 0.2% SDS at 40° C. for 30minutes). More specifically, the term is intended to refer to a DNAsequence which is at least 70% homologous to any of the sequences shownabove encoding an endoglucanase specific for xyloglucan, including atleast 75%, at least 80%, at least 85%, at least 90% or even at least 95%with any of the sequences shown above. The term is intended to includemodifications of any of the DNA sequences shown above, such asnucleotide substitutions which do not give rise to another amino acidsequence of the polypeptide encoded by the sequence, but whichcorrespond to the codon usage of the host organism into which a DNAconstruct comprising any of the DNA sequences is introduced ornucleotide substitutions which do give rise to a different amino acidsequence and therefore, possibly, a different amino acid sequence andtherefore, possibly, a different protein structure which might give riseto an endoglucanase mutant with different properties than the nativeenzyme. Other examples of possible modifications are insertion of one ormore nucleotides into the sequence, addition of one or more nucleotidesat either end of the sequence, or deletion of one or more nucleotides ateither end or within the sequence.

Endoglucanase specific for xyloglucan useful in the present inventionpreferably is one which has a XGU/BGU, XGU/CMU and/or XGU/AVIU ratio (asdefined above) of more than 50, such as 75, 90 or 100.

Furthermore, the endoglucanase specific for xyloglucan is preferablysubstantially devoid of activity towards β-glucan and/or exhibits at themost 25% such as at the most 10% or about 5%, activity towardscarboxymethyl cellulose and/or Avicell when the activity towardsxyloglucan is 100%. In addition, endoglucanase specific for xyloglucanof the invention is preferably substantially devoid of transferaseactivity, an activity which has been observed for most endoglucanasesspecific for xyloglucan of plant origin.

Endoglucanase specific for xyloglucan may be obtained from the fungalspecies A. aculeatus, as described in WO 94/14953. Microbialendoglucanases specific for xyloglucan has also been described in WO94/14953. Endoglucanases specific for xyloglucan from plants have beendescribed, but these enzymes have transferase activity and thereforemust be considered inferior to microbial endoglucanases specific forxyloglucan whenever extensive degradation of xyloglucan is desirable. Anadditional advantage of a microbial enzyme is that it, in general, maybe produced in higher amounts in a microbial host, than enzymes of otherorigins.

The xyloglucanase, when present, is incorporated into the treatingcompositions of the invention preferably at a level of from 0.0001% to2%, more preferably from 0.0005% to 0.1%, most preferred from 0.001% to0.02% pure enzyme by weight of the composition.

The above-mentioned enzymes may be of any suitable origin, such asvegetable, animal, bacterial, fungal and yeast origin. Origin canfurther be mesophilic or extremophilic (psychrophilic, psychrotrophic,thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.).Purified or non-purified forms of these enzymes may be used. Nowadays,it is common practice to modify wild-type enzymes via protein/geneticengineering techniques in order to optimize their performance efficiencyin the treating compositions of the invention. For example, the variantsmay be designed such that the compatibility of the enzyme to commonlyencountered ingredients of such compositions is increased.Alternatively, the variant may be designed such that the optimal pH,bleach or chelant stability, catalytic activity and the like, of theenzyme variant is tailored to suit the particular cleaning application.

In particular, attention should be focused on amino acids sensitive tooxidation in the case of bleach stability and on surface charges for thesurfactant compatibility. The isoelectric point of such enzymes may bemodified by the substitution of some charged amino acids, e.g. anincrease in isoelectric point may help to improve compatibility withanionic surfactants. The stability of the enzymes may be furtherenhanced by the creation of e.g. additional salt bridges and enforcingcalcium binding sites to increase chelant stability.

These optional detersive enzymes, when present, are normallyincorporated in the treating composition at levels from 0.0001% to 2% ofpure enzyme by weight of the treating composition. The enzymes can beadded as separate single ingredients (prills, granulates, stabilizedliquids, etc . . . containing one enzyme) or as mixtures of two or moreenzymes ( e.g. cogranulates).

Other suitable cleaning adjunct materials that can be added are enzymeoxidation scavengers. Examples of such enzyme oxidation scavengers areethoxylated tetraethylene polyamines.

A range of enzyme materials and means for their incorporation intosynthetic detergent compositions is also disclosed in WO 9307263 and WO9307260 to Genencor International, WO 8908694, and U.S. Pat. No.3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are further disclosedin U.S. Pat. No. 4,101,457, and in U.S. Pat. No. 4,507,219. Enzymematerials useful for liquid detergent formulations, and theirincorporation into such formulations, are disclosed in U.S. Pat. No.4,261,868.

Enzyme Stabilizers—Enzymes for use in treating compositions can bestabilized by various techniques. Enzyme stabilization techniques aredisclosed and exemplified in U.S. Pat. No. 3,600,319, EP 199,405 and EP200,586. Enzyme stabilization systems are also described, for example,in U.S. Pat. No. 3,519,570. A useful Bacillus, sp. AC13 givingproteases, xylanases and cellulases, is described in WO 9401532. Theenzymes employed herein can be stabilized by the presence ofwater-soluble sources of calcium and/or magnesium ions in the finishedcompositions which provide such ions to the enzymes. Suitable enzymestabilizers and levels of use are described in U.S. Pat. Nos. 5,705,464,5,710,115 and 5,576,282.

Builders—The treating compositions described herein preferably compriseone or more detergent builders or builder systems. When present, thecompositions will typically comprise at least about 1% builder,preferably from about 5%, more preferably from about 10% to about 80%,preferably to about 50%, more preferably to about 30% by weight, ofdetergent builder. Lower or higher levels of builder, however, are notmeant to be excluded.

Preferred builders for use in the treating compositions, particularlydishwashing compositions, described herein include, but are not limitedto, water-soluble builder compounds, (for example polycarboxylates) asdescribed in U.S. Pat. Nos. 5,695,679, 5,705,464 and 5,710,115. Othersuitable polycarboxylates are disclosed in U.S. Pat. Nos. 4,144,226,3,308,067 and 3,723,322. Preferred polycarboxylates arehydroxycarboxylates containing up to three carboxy groups per molecule,more particularly titrates.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates (see, for example,U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and3,422,137), phytic acid, silicates, carbonates (including bicarbonatesand sesquicarbonates), sulphates, and aluminosilicates.

However, non-phosphate builders are required in some locales.Importantly, the compositions herein function surprisingly well even inthe presence of the so-called “weak” builders (as compared withphosphates) such as citrate, or in the so-called “underbuilt” situationthat may occur with zeolite or layered silicate builders.

Suitable silicates include the water-soluble sodium silicates with anSiO₂:Na₂O ratio of from about 1.0 to 2.8, with ratios of from about 1.6to 2.4 being preferred, and about 2.0 ratio being most preferred. Thesilicates may be in the form of either the anhydrous salt or a hydratedsalt. Sodium silicate with an SiO₂:Na₂O ratio of 2.0 is the mostpreferred. Silicates, when present, are preferably present in thetreating compositions described herein at a level of from about 5% toabout 50% by weight of the composition, more preferably from about 10%to about 40% by weight.

Partially soluble or insoluble builder compounds, which are suitable foruse in the treating compositions, particularly granular detergentcompositions, include, but are not limited to, crystalline layeredsilicates, preferably crystalline layered sodium silicates (partiallywater-soluble) as described in U.S. Pat. No. 4,664,839, and sodiumaluminosilicates (water-insoluble). When present in treatingcompositions, these builders are typically present at a level of fromabout 1% to 80% by weight, preferably from about 10% to 70% by weight,most preferably from about 20% to 60% by weight of the composition.

Crystalline layered sodium silicates having the general formulaNaMSi_(x)O_(2x+1).yH₂O wherein M is sodium or hydrogen, x is a numberfrom about 1.9 to about 4, preferably from about 2 to about 4, mostpreferably 2, and y is a number from about 0 to about 20, preferably 0can be used in the compositions described herein. Crystalline layeredsodium silicates of this type are disclosed in EP-A-0164514 and methodsfor their preparation are disclosed in DE-A-3417649 and DE-A-3742043.The most preferred material is delta-Na₂SiO₅, available from Hoechst AGas NaSKS-6 (commonly abbreviated herein as “SKS-6”). Unlike zeolitebuilders, the Na SKS-6 silicate builder does not contain aluminum.NaSKS-6 has the delta-Na₂SiO₅ morphology form of layered silicate. SKS-6is a highly preferred layered silicate for use in the compositionsdescribed herein, but other such layered silicates, such as those havingthe general formula NaMSi_(x)O_(2x+1).yH₂O wherein M is sodium orhydrogen, x is a number from 1.9 to 4, preferably 2, and y is a numberfrom 0 to 20, preferably 0 can be used in the compositions describedherein. Various other layered silicates from Hoechst include NaSKS-5,NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As notedabove, the delta-Na₂SiO₅ (NaSKS-6 form) is most preferred for useherein. Other silicates may also be useful such as for example magnesiumsilicate, which can serve as a crispening agent in granularformulations, as a stabilizing agent for oxygen bleaches, and as acomponent of suds control systems.

The crystalline layered sodium silicate material is preferably presentin granular detergent compositions as a particulate in intimateadmixture with a solid, water-soluble ionizable material. The solid,water-soluble ionizable material is preferably selected from organicacids, organic and inorganic acid salts and mixtures thereof.

Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders have the empirical formula:

[M_(z)(AlO₂)_(y) ].xH₂O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264. Preferably, the aluminosilicate builder is an aluminosilicatezeolite having the unit cell formula:

Na_(z)[(AlO₂)_(z)(SiO₂)_(y) ].xH₂O

wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to0.5 and x is at least 5, preferably 7.5 to 276, more preferably from 10to 264. The aluminosilicate builders are preferably in hydrated form andare preferably crystalline, containing from about 10% to about 28%, morepreferably from about 18% to about 22% water in bound form.

These aluminosilicate ion exchange materials can be crystalline oramorphous in structure and can be naturally-occurring aluminosilicatesor synthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669. Preferredsynthetic crystalline aluminosilicate ion exchange materials usefulherein are available under the designations Zeolite A, Zeolite B,Zeolite P, Zeolite X, Zeolite AX, Zeolite MAP and Zeolite HS andmixtures thereof. In an especially preferred embodiment, the crystallinealuminosilicate ion exchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂ ].xH₂O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter. Zeolite X has the formula:

Na₈₆[(AlO₂)₈₆(SiO₂)₁₀₆].276H₂O

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the detergent compositions described herein are the3,3-dicarboxy oxa-1,6-hexanedioates and the related compounds disclosedin U.S. Pat. No. 4,566,984. Useful succinic acid builders include theC₅-C₂₀ alkyl and alkenyl succinic acids and salts thereof. Aparticularly preferred compound of this type is dodecenylsuccinic acid.Specific examples of succinate builders include: laurylsuccinate,myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),2-pentadecenylsuccinate, and the like. Laurylsuccinates are thepreferred builders of this group, and are described in European PatentApplication 86200690.5/0,200,263, published Nov. 5, 1986.

Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

Dispersants—One or more suitable polyalkyleneimine dispersants may beincorporated into the treating compositions of the present invention.Examples of such suitable dispersants can be found in European PatentApplication Nos. 111,965, 111,984, and 112,592; U.S. Pat. Nos.4,597,898, 4,548,744, and 5,565,145. However, any suitable clay/soildispersent or anti-redepostion agent can be used in the treatingcompositions of the present invention.

In addition, polymeric dispersing agents which include polymericpolycarboxylates and polyethylene glycols, are suitable for use in thepresent invention. Unsaturated monomeric acids that can be polymerizedto form suitable polymeric polycarboxylates include acrylic acid, maleicacid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. Particularlysuitable polymeric polycarboxylates can be derived from acrylic acid.Such acrylic acid-based polymers which are useful herein are thewater-soluble salts of polymerized acrylic acid. The average molecularweight of such polymers in the acid form preferably ranges from about2,000 to 10,000, more preferably from about 4,000 to 7,000 and mostpreferably from about 4,000 to 5,000. Water-soluble salts of suchacrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in U.S. Pat. No.3,308,067.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000 to 100,000, more preferably fromabout 5,000 to 75,000, most preferably from about 7,000 to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:1, more preferably from about 10:1 to2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers caninclude, for example, the alkali metal, ammonium and substitutedammonium salts. Soluble acrylate/maleate copolymers of this type areknown materials which are described in European Patent Application No.66915, published Dec. 15, 1982, as well as in EP 193,360, published Sep.3, 1986, which also describes such polymers comprisinghydroxypropylacrylate. Still other useful dispersing agents include themaleic/acrylic/vinyl alcohol terpolymers. Such materials are alsodisclosed in EP 193,360, including, for example, the 45/45/10 terpolymerof acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Soil Release Agents—The treating compositions according to the presentinvention may optionally comprise one or more soil release agents. Ifutilized, soil release agents will generally comprise from about 0.01%,preferably from about 0.1%, more preferably from about 0.2% to about10%, preferably to about 5%, more preferably to about 3% by weight, ofthe composition. Nonlimiting examples of suitable soil release polymersare disclosed in: U.S. Pat. Nos. 5,728,671; 5,691,298; 5,599,782;5,415,807; 5,182,043; 4,956,447; 4,976,879; 4,968,451; 4,925,577;4,861,512; 4,877,896; 4,771,730; 4,711,730; 4,721,580; 4,000,093;3,959,230; and 3,893,929; and European Patent Application 0 219 048.

Further suitable soil release agents are described in U.S. Pat. Nos.4,201,824; 4,240,918; 4,525,524; 4,579,681; 4,220,918; and 4,787,989; EP279,134 A; EP 457,205 A; and DE 2,335,044.

Chelating Agents—The treating compositions of the present inventionherein may also optionally contain a chelating agent which serves tochelate metal ions and metal impurities which would otherwise tend todeactivate the bleaching agent(s). Useful chelating agents can includeamino carboxylates, phosphonates, amino phosphonates,polyfunctionally-substituted aromatic chelating agents and mixturesthereof. Further examples of suitable chelating agents and levels of useare described in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,728,671 and5,576,282.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builderuseful with, for example, insoluble builders such as zeolites, layeredsilicates and the like.

If utilized, these chelating agents will generally comprise from about0.1% to about 15%, more preferably from about 0.1% to about 3.0% byweight of the treating compositions herein.

Suds suppressor—Another optional ingredient is a suds suppressor,exemplified by silicones, and silica-silicone mixtures. Examples ofsuitable suds suppressors are disclosed in U.S. Pat. Nos. 5,707,950 and5,728,671. These suds suppressors are normally employed at levels offrom 0.001% to 2% by weight of the composition, preferably from 0.01% to1% by weight.

Softening agents—Fabric softening agents can also be incorporated intothe treating compositions of the present invention. Inorganic softeningagents are exemplified by the smectite clays disclosed in GB-A-1 400 898and in U.S. Pat. No. 5,019,292. Organic softening agents include thewater insoluble tertiary amines as disclosed in GB-A-1 514 276 andEP-B-011 340 and their combination with mono C12-C14 quaternary ammoniumsalts are disclosed in EP-B-026 527 and EP-B-026 528 and di-long-chainamides as disclosed in EP-B-0 242 919. Other useful organic ingredientsof fabric softening systems include high molecular weight polyethyleneoxide materials as disclosed in EP-A-0 299 575 and 0 313 146.

Particularly suitable fabric softening agents are disclosed in U.S. Pat.Nos. 5,707,950 and 5,728,673.

Levels of smectite clay are normally in the range from 2% to 20%, morepreferably from 5% to 15% by weight, with the material being added as adry mixed component to the remainder of the formulation. Organic fabricsoftening agents such as the water-insoluble tertiary amines or dilongchain amide materials are incorporated at levels of from 0.5% to 5% byweight, normally from 1% to 3% by weight whilst the high molecularweight polyethylene oxide materials and the water soluble cationicmaterials are added at levels of from 0.1% to 2%, normally from 0.15% to1.5% by weight. These materials are normally added to the spray driedportion of the composition, although in some instances it may be moreconvenient to add them as a dry mixed particulate, or spray them asmolten liquid on to other solid components of the composition.

Biodegradable quaternary ammonium compounds as described in EP-A-040 562and EP-A-239 910 have been presented as alternatives to thetraditionally used di-long alkyl chain ammonium chlorides and methylsulfates.

Non-limiting examples of softener-compatible anions for the quaternaryammonium compounds and amine precursors include chloride or methylsulfate.

Due transfer inhibition—The treating compositions of the presentinvention can also include compounds for inhibiting dye transfer fromone fabric to another of solubilized and suspended dyes encounteredduring fabric laundering and conditioning operations involving coloredfabrics.

Polymeric Dye Transfer Inhibiting Agents

The treating compositions according to the present invention can alsocomprise from 0.001% to 10%, preferably from 0.01% to 2%, morepreferably from 0.05% to 1% by weight of polymeric dye transferinhibiting agents. Said polymeric dye transfer inhibiting agents arenormally incorporated into treating compositions in order to inhibit thetransfer of dyes from colored fabrics onto fabrics washed therewith.These polymers have the ability to complex or adsorb the fugitive dyeswashed out of dyed fabrics before the dyes have the opportunity tobecome attached to other articles in the wash.

Especially suitable polymeric dye transfer inhibiting agents arepolyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidonesand polyvinylimidazoles or mixtures thereof. Examples of such dyetransfer inhibiting agents are disclosed in U.S. Pat. Nos. 5,707,950 and5,707,951.

Additional suitable dye transfer inhibiting agents include, but are notlimited to, cross-linked polymers. Cross-linked polymers are polymerswhose backbone are interconnected to a certain degree; these links canbe of chemical or physical nature, possibly with active groups n thebackbone or on branches; cross-linked polymers have been described inthe Journal of Polymer Science, volume 22, pages 1035-1039.

In one embodiment, the cross-linked polymers are made in such a way thatthey form a three-dimensional rigid structure, which can entrap dyes inthe pores formed by the three-dimensional structure. In anotherembodiment, the cross-linked polymers entrap the dyes by swelling. Suchcross-linked polymers are described in the co-pending European patentapplication 94870213.9.

Addition of such polymers also enhances the performance of the enzymesaccording the invention.

Hydrogen Bond Breaking Agents—Suitable hydrogen bond breaking agentsincluding, but not limited to, plant expansin and urea can optionally beincorporated into the treating compositions of the present invention.

pH and Buffering Variation—Many of the treating compositions describedherein will be buffered, i.e., they are relatively resistant to pH dropin the presence of acidic soils. However, other compositions herein mayhave exceptionally low buffering capacity, or may be substantiallyunbuffered. Techniques for controlling or varying pH at recommendedusage levels more generally include the use of not only buffers, butalso additional alkalis, acids, pH-jump systems, dual compartmentcontainers, etc., and are well known to those skilled in the art.

Other Materials—Other cleaning adjunct materials optionally included inthe treating compositions of the present invention can include one ormore materials for assisting or enhancing cleaning performance,treatment of the substrate to be cleaned, or designed to improve theaesthetics of the compositions. Adjuncts which can also be included incompositions of the present invention, at their conventionalart-established levels for use (generally, adjunct materials comprise,in total, from about 30% to about 99.9%, preferably from about 70% toabout 95%, by weight of the compositions), include other activeingredients such as clay soil removal/anti-redeposition agents,brighteners, dyes, perfumes, structure elasticizing agents, carriers,hydrotropes, processing aids, fillers, germicides, alkalinity sources,solubilizing agents and/or pigments. Suitable examples of such othercleaning adjunct materials and levels of use are found in U.S. Pat. Nos.5,576,282, 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and5,646,101.

The following examples are meant to exemplify compositions of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention. In the treating compositions, theenzyme levels are expressed by percent of pure enzyme by weight of thetotal composition and unless otherwise specified, the cleaning adjunctmaterials are expressed as percent of cleaning adjunct materials byweight of the total compositions. The polysaccharides can be anysuitable polysaccharide disclosed hereinabove.

Further, in the following examples some abbreviations known to those ofordinary skill in the art are used, consistent with the disclosure setforth herein, and/or are defined in below.

LAS Sodium linear C₁₂ alkyl benzene sulphonate TAS Sodium tallow alkylsulphate CXYAS Sodium C_(1X)-C_(1Y) alkyl sulfate 25EY A C₁₂-C₁₅predominantly linear primary alcohol condensed with an average of Ymoles of ethylene oxide CXYEZ A C_(1X)-C_(1Y) predominantly linearprimary alcohol condensed with an average of Z moles of ethylene oxideXYEZS C_(1X)-C_(1Y) sodium alkyl sulfate condensed with an average of Zmoles of ethylene oxide per mole QAS R₂.N⁺(CH₃)₂(C₂H₄OH) with R₂ =C₁₂-C₁₄ Soap Sodium linear alkyl carboxylate derived from a 80/20mixture of tallow and coconut oils. Nonionic C₁₃-C₁₅ mixedethoxylated/propoxylated fatty alcohol with an average degree ofethoxylation of 3.8 and an average degree of propoxylation of 4.5 soldunder the tradename Plurafac LF404 by BASF Gmbh. CFAA C₁₂-C₁₄ alkylN-methyl glucamide TFAA C₁₆-C₁₈ alkyl N-methyl glucamide TPKFA C12-C14topped whole cut fatty acids. DEQA Di-(tallow-oxy-ethyl) dimethylammonium chloride. Neodol 45-13 C14-C15 linear primary alcoholethoxylate, sold by Shell Chemical CO. Silicate Amorphous SodiumSilicate (SiO₂:Na₂O ratio = 2.0) NaSKS-6 Crystalline layered silicate offormula δ-Na₂Si₂O₅. Carbonate Anhydrous sodium carbonate with a particlesize between 200 μm and 900 μm. Bicarbonate Anhydrous sodium bicarbonatewith a particle size between 400 μm and 1200 μm. STPP Anhydrous sodiumtripolyphosphate MA/AA Copolymer of 1:4 maleic/acrylic acid, averagemolecular weight about 70,000-80,000 Zeolite A Hydrated SodiumAluminosilicate of formula Na₁₂(AlO₂SiO₂)₁₂ .27H₂O having a primaryparticle size in the range from 0.1 to 10 micrometers Citrate Tri-sodiumcitrate dihydrate of activity 86,4% with a particle size distributionbetween 425 μm and 850 μm. Citric Anhydrous citric acid PB1 Anhydroussodium perborate monohydrate bleach, empirical formula NaBO₂.H₂O₂ PB4Anhydrous sodium perborate tetrahydrate Percarbonate Anhydrous sodiumpercarbonate bleach of empirical formula 2Na₂CO₃.3H₂O₂ TAED Tetraacetylethylene diamine. NOBS Nonanoyloxybenzene sulfonate in the form of thesodium salt. Photoactivated Bleach Sulfonated zinc phalocyanineencapsulated in dextrin soluble polymer. Protease Proteolytic enzymedescribed hereinbefore. Amylase Amlylolytic enzyme describedhereinbefore. Lipase Lipolytic enzyme described hereinbefore. CellulaseCellulytic enzyme described hereinbefore. CMC Sodium carboxymethylcellulose. HEDP 1,1-hydroxyethane diphosphonic acid. DETPMP Diethylenetriamine penta (methylene phosphonic acid), marketed by Monsanto underthe Trade name Dequest 2060. PVNO Poly(4-vinylpyridine)-N-Oxide. PVPVIPoly(4-vinylpyridine)-N-oxide/copolymer of vinyl-imidazole andvinyl-pyrrolidone. Brightener 1 Disodium4,4″-bis(2-sulphostyryl)biphenyl. Brightener 2 Disodium4,4″-bis(anilino-6-morpholino-1.3.5-triazin-2-yl)stilbene-2:2″-sulfonate. Silicone antifoam Polydimethylsiloxane foamcontroller with siloxane- oxyalkylene copolymer as dispersing agent witha ratio of said foam controller to said dispersing agent of 10:1 to100:1. Granular Suds 12% Silicone/silica, 18% stearyl alcohol, 70%starch in Suppressor granular form SRP 1 Sulfobenzoyl or sodiumisethionate end capped esters with oxyethylene oxy and terephtaloylbackbone. SRP 2 Diethoxylated poly (1,2 propylene terephtalate) shortblock polymer. Sulphate Anhydrous sodium sulphate. HMWPEO High molecularweight polyethylene oxide

EXAMPLE I

Wt. % Ingredients Ia Ib Ic Id Ie If Polysaccharide 0.5 1 0.2 0.5 0.5 0.5  Volatile — — — 0.1 — — Perfume A⁽¹⁾ Substantive — — — — 0.03 —Perfume B⁽²⁾ Hydrophilic — — — — — 0.05 Perfume C⁽³⁾ Poly- — — — 0.20.1  — sorbate 60⁽⁴⁾ Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppmDeionized Bal. Bal. Bal. Bal. Bal. Bal. Water ⁽¹⁾Perfume contains mainlyingredients having a boiling point of less than about 250° C. ⁽²⁾Perfumecontains mainly ingredients having a boiling point of about 250° C. orhigher. ⁽³⁾Perfume contains mainly ingredients having a ClogP of about3.0 or less. ⁽⁴⁾A mixture of stearate esters of sorbitol and sorbitolanhydride, consisting predominantly of the monoester, condensed withabout 20 moles of ethylene oxide.

EXAMPLE II

Wt. % Ingredients IIa IIb IIc IId IIe IIf Polysaccharide 1 2 0.5 1   1  1   Perfume A — — — — 1   — Perfume B — — — 0.3 — — Perfume C — — — — —1.5 Polysorbate 60 — — — 0.5 1.5 1   Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3ppm 3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal. Water Concentratedcompositions of Examples II are diluted with water to obtain usagecompositions for, e.g., spraying, soaking, dipping, cellulosic fabrics.

EXAMPLE III

Wt. % Ingredients IIIa IIIb IIIc IIId IIIe Polysaccharide 1   2   0.51   1   LiBr 3   — — 2   2   Silicone Emulsion⁽⁵⁾ — 1.5 — — 2.0  D5Volatile Silicone — — 0.5 0.5  — Perfume A — — — — 0.03 Perfume B — — —0.05 — Perfume C 0.03 — — — — Polysorbate 60 — — — 0.1  0.05 SilwetL-7602 — — — 0.5  — Silwet L-7622 — — — — 0.3  Kathon CG 3 ppm 3 ppm 3ppm 3 ppm 3 ppm Deionized Water Bal. Bal. Bal. Bal. Bal. ⁽⁵⁾DC-2-5932silicone microemulsion (25% active) from Dow Corning, with a particlesize of about 24 nm, a cationic surfactant system, and a silicone withan internal phase viscosity of about 1,200 cps.

EXAMPLE IV

Wt. % Ingredients IVa IVb IVc IVd Ive IVf Polysaccharide 1   2  0.5  1  1   0.5  Copolymer A⁽⁶⁾ 0.4  — — — — 0.5  Copolymer B⁽⁷⁾ — 0.5  — 0.3  —— Copolymer C⁽⁸⁾ — — 0.6  — 0.5  — LiBr — — — 3   — 2   Silicone — — — —1.5  — Emulsion⁽⁵⁾ D5 Volatile — — — — — 0.5  Silicone Perfume A 0.06 —— — — 0.07 Perfume B — 0.03 — 0.03 — — Perfume C — — 0.04 — 0.03 —Polysorbate 60 0.1  0.1  0.03 0.1  0.1  0.1  Silwet L-7600 — — — 0.5  —— Silwet L-7602 — — — — — 0.7  Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal. Water ⁽⁵⁾DC-2-5932 siliconemicroemulsion (25% active) from Dow Corning, with a particle size ofabout 24 nm, a cationic surfactant system, and a silicone with aninternal phase viscosity of about 1,200 cps. ⁽⁶⁾Acrylic acid/tert-butylacrylate copolymer, with an approximate acrylic acid/tert-butyl acrylateweight ratio of about 25/75 and an average molecular weight of fromabout 70,000 to about 100,000. ⁽⁷⁾Acrylic acid/tert-butyl acrylatecopolymer, with an approximate acrylic acid/tert-butyl acrylate weightratio of about 35/65 and an average molecular weight of from about60,000 to about 90,000. ⁽⁸⁾Acrylic acid/tert-butyl acrylate copolymer,with an approximate acrylic acid/tert-butyl acrylate weight ratio ofabout 20/80 and an average molecular weight of from about 80,000 toabout 110,000.

EXAMPLE V

Wt. % Ingredients Va Vb Vc Vd Ve Vf Polysaccharide 1   2   0.5  1   1  0.5  Copolymer 0.4  — — — 2   0.25 D⁽⁹⁾ Copolymer — 0.5  — — — 0.25E⁽¹⁰⁾ Copolymer — — 0.4  — — — F⁽¹¹⁾ Copolymer — — — 0.5  — — G⁽¹²⁾ D5Volatile — 0.25 — — — — Silicone PDMS 10,000 — — — 0.3  — — cst Silicone— — 1   — 2   — Emulsion B⁽¹³⁾ Perfume A 0.06 — — — — 0.07 Perfume B —0.03 — 0.03 — — Perfume C — — 0.04 — 0.5 — Polysorbate 60 0.1  0.1  —0.1  0.5 0.1  Neodol 23-3 — 0.25 — 0.2  — — Neodol 25-3 — — 0.3  — 0.30.25 Silwet L-77 — 0.7  — 1   — — Silwet L-7604 — — 0.5  — — 0.7  KathonCG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Deionized Bal. Bal. Bal. Bal.Bal. Bal. Water ⁽⁹⁾Acrylic acid/tert-butyl acrylate copolymer, with anapproximate acrylic acid/tert-butyl acrylate weight ratio of about 23/77and an average molecular weight of about 82,000. ⁽¹⁰⁾Silicone-containingcopolymer having t-butyl acrylate/acrylic acid/(polydimethylsiloxanemacromer, 10,000 approximate molecular weight) monomer at an approximate63/20/17 weight ratio, and of an average molecular weight of about130,000. ⁽¹¹⁾Silicone-containing copolymer having t-butylacrylate/acrylic acid/(polydimethylsiloxane macromer, 10,000 approximatemolecular weight) monomer at an approximate 65/25/10 weight ratio, andof average molecular weight of about 200,000. ⁽¹²⁾Silicone-containingcopolymer having (N,N,N-trimethyiammonioethyl methacrylatechloride)/N,N-dimethylacrylamide/(PDMS macromer - 15,000 approximatemolecular weight) at an approximate 40/40/20 weight ratio, and ofaverage molecular weight of about 150,000. ⁽¹³⁾DC-1550 siliconemicroemulsion (25% active) from Dow Corning, with a particle size ofabout 50 nm, an anionic/nonionic surfactant system, and a silicone withan internal phase viscosity of about 100,000 cps.

The composition of Example Ve is a concentrated composition, to bediluted for use.

EXAMPLE VI

Wt % Ingredients VIa VIb VIc VId VIe VIf Polysaccharide 1   2   0.5  1  1   0.5  HPBCD⁽¹⁴⁾ 1   — 0.5  — 0.5  — RAMEB⁽¹⁵⁾ — 1   — — — — HPACD⁽¹⁶⁾— — 0.5  — — — α-Cyclodextrin — — — — 0.5  0.5  b-Cyclodextrin — — — 0.5— 0.5  ZnCl₂ — 1.0  — 1.0 — 1   Silwet L-7657 — — — — — — Perfume C 0.1 0.07 0.05 — 0.1  0.05 Propylene 0.06 — 0.05 — 0.03 — glycol Kathon CG 3ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm HCl — to — to — to pH 4.5 pH 5 pH 4.5Distilled Bal. Bal. Bal. Bal. Bal. Bal. water ⁽¹⁴⁾Hydroxypropylbeta-cyclodextrin. ⁽¹⁵⁾Randomly methylated beta-cyclodextrin.⁽¹⁶⁾Hydroxypropyl alpha-cyclodextrin.

EXAMPLE VII

Wt % Ingredients VIIa VIIb VIIc VIId VIIe VIIf Polysaccharide 1   2  0.5  1   1   0.5  HPBCD 1.0  — — — — — RAMEB — 1.0  — — — — SilwetL-7604 0.3  0.2  0.2  — — 0.1  Chlorhexidine 0.01 — — — — 0.005 Barquat— — 0.03 — — — 4250⁽¹⁷⁾ Bardac 2050⁽¹⁸⁾ — — — 0.03 0.03 — Perfume C 0.080.08 0.05 0.05 — — HCl to — — — — — pH 4 Kathon CG 3 ppm 3 ppm 3 ppm 3ppm 3 ppm 3 ppm Distilled Bal. Bal. Bal. Bal. Bal. Bal. water⁽¹⁷⁾Benzalkonium chloride, 50% solution. ⁽¹⁸⁾Dioctyl dimethyl ammoniumchloride, 50% solution.

The compositions of Examples I to VII (diluted when appropriate) aresprayed onto clothing using, e.g., the TS-800 sprayer from Calmar, andallowed to evaporate off of the clothing.

The compositions of Examples I to VII (diluted when appropriate) aresprayed onto clothing, using a blue inserted Guala ® trigger sprayer,available from Berry Plastics Corp. and a cylindrical Euromist II ® pumpsprayer available from Seaquest Dispensing, respectively, and allowed toevaporate off of the clothing.

The compositions of Examples I to VII (diluted when appropriate)contained in rechargeable battery-operated Solo Spraystar sprayers aresprayed onto large surfaces of fabric, such as several pieces ofclothing, and allowed to evaporate off of these surfaces. The level ofcoverage is uniform and the ease and convenience of application issuperior to conventional manually operated trigger sprayers.

The compositions of Examples I to VII (diluted when appropriate) areused for soaking or dipping of fabrics which are then optionally wrungor squeezed to remove excess liquid and subsequently dried.

Following are Examples for rinse added fabric care compositions inaccordance with the present invention:

EXAMPLE VIII

Wt % Ingredients VIIIa VIIIb VIIIc VIIId VIIIe Polysaccharide 1   2  2   3   2   Fabric softener A⁽¹⁹⁾ 4.5  — — — — Fabric softener B⁽²⁰⁾ —24   — — — Fabric softener C⁽²¹⁾ — — 26   — — Fabric softener D⁽²²⁾ — —— 28   28   Fabric softener E⁽²³⁾ 3.4  — — — — 1,2-Hexanediol — — 18   —— 2-Ethyl-1,3-hexanediol — — — 6   — Neodol 91-8 — — — 5   3   PluronicL-350 — — — 1   Hexylene glycol — — — — 3   Hexylene glycol (from — — —2.5  2.5  softener active) Ethanol (from softener — 4.2  4.6  2.3  2.3 active) Perfume B 0.3  1.3  1.3  2   1.2  Tenox 6 antioxidant 0.02 0.040.04 0.04 0.04 CaCl₂ 0.05 0.4  0.5  — 2   MgCl₂ — — — 1.6  — HCl to toto to to pH 6 pH 3.5 pH 3.5 pH 3 pH 3 Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm3 ppm Deionized water and Bal. Bal. Bal. Bal. Bal. other minoringredients ⁽¹⁹⁾Di(hydrogenated tallowyl) dimethyl ammoniumchloride/hydrogenated tallowyl trimethyl ammonium chloride blend ofabout 83:17 weight ratio. ⁽²⁰⁾Di(acyloxyethyl) dimethyl ammoniumchloride wherein the acyl group is derived from soft tallow fatty acidsand with a diester-to-monoester weight ratio of about 11:1.⁽²¹⁾Di(acyloxyethyl) dimethyl ammonium chloride wherein the acyl groupis derived from partially hydrogenated canola fatty acids and with adiester-to-monoester weight ratio of about 11:1.⁽²²⁾Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfatewherein the acyl group is derived from partially hydrogenated canolafatty acids. ⁽²³⁾1-Tallow(amidoethyl)-2-tallowimidazoline.

EXAMPLE IX

Wt % Ingredients IXa IXb IXc IXd IXe IXf Polysaccharide 1   2   2   2  3 3   Fabric softener 4.5 — — — — — A⁽¹⁹⁾ Fabric softener — 22  25  25 — — B⁽²⁰⁾ Fabric softener 3.4 — — — — — E⁽²³⁾ PVP K-15⁽²⁴⁾ 1   3   — — 5— PVNO⁽²⁵⁾ — — 1   — — — Cellulase⁽²⁶⁾ — — — 1   — 2   Perfume B 0.4 1.31.3 1.3 2 — Perfume C — — — — — 1.5 Polysorbate 60 — — — — 5 1   HCl topH to pH to pH to pH — — 5 3.5 3.5 3.5 Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm3 ppm 3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal. water and minoringredients ⁽¹⁹⁾Di(hydrogenated tallowyl) dimethyl ammoniumchloride/hydrogenated tallowyl trimethyl ammonium chloride blend ofabout 83:17 weight ratio. ⁽²⁰⁾Di(acyloxyethyl) dimethyl ammoniumchloride wherein the acyl group is derived from soft tallow fatty acidsand with a diester-to-monoester weight ratio of about 11:1.⁽²³⁾1-Tallow(amidoethyl)-2-tallowimidazoline. ⁽²⁴⁾Polyvinylpyrrolidonewith an average molecular weight of about 10,000.⁽²⁵⁾Poly(4-vinylpyridine-N-oxide) with an average molecular weight ofabout 25,000. ⁽²⁶⁾The cellulase consists essentially of a homogeneousendoglucanase component, which is immunoreactive with an antibody raisedagainst a highly purified 43 kD cellulase derived from Humicolainsolens, DMS 1800, or which is homologous to said 43 kD endoglucanase;the cellulase solution used provides about 5,000 CEVU's per gram.Following are Examples for laundry detergent fabric care compositions inaccordance with the present invention:

EXAMPLE X

Wt % Ingredients Xa Xb LAS 8 8 C25E3 3.4 3.4 QAS — 0.8 Zeolite A 17 17Carbonate 13 24 Silicate 1.4 3 Sulfate 25 15 PB4 9 8 TAED 1.5 1.5 DETPMP0.25 0.25 HEDP 0.3 0.3 Polysaccharide 3 5 Protease 26 ppm 26 ppm MA/AA0.3 0.3 CMC 0.2 0.2 Photoactivated Bleach — 10 ppm Brightener 0.09 0.09Perfume 0.3 0.3 Silicone antifoam 0.5 0.5 Moisture and MiscellaneousBalance Balance

EXAMPLE XI

Nil bleach-containing laundry detergent fabric care compositions ofparticular use in the washing if colored clothing:

Wt % Ingredients XIa XIb Blown Powder Zeolite A 14 14 Sodium sulfate —13 LAS 2.8 3 DETPMP 0.4 0.5 CMC 0.4 0.4 MA/AA 3.8 4 Agglomerates LAS 5.55 TAS 3 2 Silicate 4 4 Zeolite A 9 13 Carbonate 9 7 Spray On Perfume 0.30.3 C45E7 4 4 C25E3 1.8 1.8 Dry additives Citrate 10 — Bicarbonate 6.5 3Carbonate 7.5 5 PVPVI/PVNO 0.5 0.5 Polysaccharide 3 2 Protease 0.0260.016 Lipase 0.009 0.009 Amylase 0.005 — Cellulase 0.006 0.006 Siliconeantifoam 4 3 Moisture and Miscellaneous Balance Balance

EXAMPLE XII

Examples of liquid detergent fabric care compositions according to thepresent invention:

Wt % Ingredients XIIa XIIb XIIc XIId XIIe LAS 9 8 — 22 — C25AS 4 2 9 —12 C25E3S 1 — 3 — 3.5 C25E7 6 12 2.5 — 3.5 TFAA — — 4.5 — 7.5 QAS — — —3 — TPKFA 2 12 2 — 5.5 Canola fatty acids — — 5 — 4 Citric 2 1 1.5 1 1Dodecenyl/tetradecenyl 10 — — 14 — succinic acid Oleic acid 4 1 — 1 —Ethanol 4 6 2 6 2 1,2 Propanediol 4 2 6 6 10 Mono Ethanol Amine — — 5 —8 Tri Ethanol Amine — 7 — — — NaOH (pH) 8 7.5 7.5 8 8 Ethoxylatedtetraethylene 0.5 0.5 0.2 — 0.3 pentamine DETPMP 1 0.5 1 2 — SRP 2 0.30.3 0.1 — 0.1 PVNO — — — — 0.1 Polysaccharide 1 2 2 3 1 Protease 50 ppm40 ppm 30 ppm 0.08 60 ppm Lipase — —  2 ppm — 30 ppm Amylase 20 ppm 50ppm 40 ppm 20 ppm 50 ppm Cellulase — —  1 ppm —  4 ppm Boric acid 0.1 —2 1 2.5 Na formate — 1 — — — Ca chloride — — 0.01 — — Bentonite clay — —— 3.5 — Suspending clay SD3 — — — 0.6 — Water and Miscellaneous Bal.Bal. Bal. Bal. Bal.

EXAMPLE XIII

Examples of syndet bar fabric detergent fabric care compositions inaccord with the present invention:

Wt % Ingredients XIVa XIVb C26 As 18 18 CFAA 5 5 LAS(C11-13) 10 10Sodium carbonate 22 25 Sodium pyrophosphate 6 6 STPP 6 6 Zeolite A 5 5CMC 0.2 0.2 Polyacrylate (MW 1400) 0.2 0.2 Coconut monoethanolamide 5 5Polysaccharide 5 3 Amylase — 0.02 Protease — 0.3 Perfume 0.2 0.2Brightener 0.1 0.1 CaSO₄ 1 1 MgSO₄ 1 1 Water 4 4 Filler Balance BalanceCan be selected from convenient materials as CaCO₃, talc, clay,(Kaolinite, Smectite), silicates, and the like.

EXAMPLE XIV

Examples of syndet bar fabric detergent fabric care compositions inaccord with the present invention:

Wt. % Ingredients XIVa XIVb C26 AS 20.00 20.00 CFAA 5.0 5.0 LAS(C11-13)10.0 10.0 Sodium carbonate 25.0 25.0 Sodium pyrophosphate 7.0 7.0 STPP7.0 7.0 Zeolite A 5.0 5.0 CMC 0.2 0.2 Polyacrylate (MW 1400) 0.2 0.2Coconut monoethanolamide 5.0 5.0 Polysaccharide 3 5 Amylase 0.01 0.02Protease 0.3 — Brightener, perfume 0.2 0.2 CaSO₄ 1.0 1.0 MgSO₄ 1.0 1.0Water 4.0 4.0 Filler*: balance to 100%

EXAMPLE XV

The following detergent formulations, according to the presentinvention, are prepared where XVa and XVc are phosphorus-containingdetergent compositions, and XVb is a zeolite-containing detergentcomposition:

XVa XVb XVc Blown Powder: STPP 24.0 — 24.0 Zeolite A — 24.0 — C45AS 9.06.0 13.0 MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 — — Silicate 7.0 3.03.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DETPMP 0.40.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone antifoam0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Dry additives: Carbonate 6.0 13.0 15.0PB4 18.0 18.0 10.0 PB1 4.0 4.0 0 TAED 3.0 3.0 1.0 Photoactivated bleach0.02 0.02 0.02 Polysaccharide 1 2 1 Protease 0.01 0.01 0.01 Lipase 0.0090.009 — Amylase 0.002 — 0.001 Dry mixed sodium sulfate 3.0 3.0 5.0Balance (Moisture & 100.0 100.0 100.0 Miscellaneous) Density (g/litre)630 670 670

EXAMPLE XVI

The following nil bleach-containing detergent formulations of particularuse in the washing of colored clothing, according to the presentinvention are prepared:

XVIa XVIb XVIc Blown Powder Zeolite A 15.0 15.0 — Sodium sulfate 0.0 5.0— LAS 3.0 3.0 — DETPMP 0.4 0.5 — CMC 0.4 0.4 — MA/AA 4.0 4.0 —Agglomerates C45AS — — 11.0 LAS 6.0 5.0 — TAS 3.0 2.0 — Silicate 4.0 4.0— Zeolite A 10.0 15.0 13.0 CMC — — 0.5 MA/AA — — 2.0 Carbonate 9.0 7.07.0 Spray On Perfume 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dryadditives MA/AA — — 3.0 NaSKS-6 — — 12.0 Citrate 10.0 — 8.0 Bicarbonate7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 Polysaccharide2 2 3 Protease 0.026 0.016 0.047 Lipase 0.009 — 0.009 Amylase 0.0050.005 — Cellulase 0.006 0.006 — Silicone antifoam 5.0 5.0 5.0 Dryadditives Sodium sulfate 0.0 9.0 0.0 Balance (Moisture and 100.0 100.0100.0 Miscellaneous Density (g/litre) 700 7000 700

EXAMPLE XVII

The following liquid detergent formulations, according to the presentinvention are prepared:

XVIIa XVIIb XVIIc XVIId XVIIe XVIIf XVIIg XVIIh LAS 10.0 13.0 9.0 — 25.0— — — C25AS 4.0 1.0 2.0 10.0 — 13.0 18.0 15.0 C25E3S 1.0 — — 3.0 — 2.02.0 4.0 C25E7 6.0 8.0 13.0 2.5 — — 4.0 4.0 TFAA — — — 4.5 — 6.0 8.0 8.0QAS — — — — 3.0 1.0 — — TPKFA 2.0 — 13.0 2.0 — 15.0 7.0 7.0 Rapeseedfatty — — — 5.0 — — 4.0 4.0 acids Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0Dodecenyl/ 12.0 10.0 — — 15.0 — — — tetradecenyl succinic acid Oleicacid 4.0 2.0 1.0 — 1.0 — — — Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13. Mono Ethanol — — — 5.0 — —9.0 9.0 Amine Tri Ethanol — — 8 — — — — — Amine NaOH (pH) 8.0 8.0 7.67.7 8.0 7.5 8.0 8.2 Ethoxylated 0.5 — 0.5 0.2 — — 0.4 0.3 tetraethylenepentamine DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 — SRP 2 0.3 — 0.3 0.1 — —0.2 0.1 PVNO — — — — — — — 0.10 Polysaccharide 0.01 1.0 10.0 2 3 5 5 1.0Protease .005 .005 .004 .003 0.08 .005 .003 .006 Lipase — .002 — .0002 —— .003 .003 Amylase .002 — — .004 .002 .008 .005 .005 Cellulase — — —.0001 — — .0004 .0004 Boric acid 0.1 0.2 — 2.0 1.0 1.5 2.5 2.5 Naformate — — 1.0 — — — — — Ca chloride — 0.015 — 0.01 — — — — Bentoniteclay — — — — 4.0 4.0 — — Suspending clay — — — — 0.6 0.3 — — SD3 Balance100 100 100 100 100 100 100 100 Moisture and Miscellaneous

EXAMPLE XVIII

Granular Fabric Cleaning Composition Example No. Component A B C DPolysaccharide 0.5 0.2 1 2 Protease 0.10 0.20 0.03 0.05 C₁₃ linear alkylbenzene sulfonate 22.00 22.00 22.00 22.00 Phosphate (as sodium 23.0023.00 23.00 23.00 tripolyphosphates) Sodium carbonate 23.00 23.00 23.0023.00 Sodium silicate 14.00 14.00 14.00 14.00 Zeolite 8.20 8.20 8.208.20 Chelant (diethylaenetriamine- 0.40 0.40 0.40 0.40 pentaacetic acid)Sodium sulfate 5.50 5.50 5.50 5.50 Water balance to 100%

EXAMPLE XIX

Granular Fabric Cleaning Composition Example No. Component A B C DPolysaccharide 1 3 5 0.4 Protease 0.10 0.20 0.03 0.05 C₁₂ alkyl benzenesulfonate 12.00 12.00 12.00 12.00 Zeolite A (1-10 micrometer) 26.0026.00 26.00 26.00 C_(12-C14) secondary (2,3) alkyl sulfate, 5.00 5.005.00 5.00 Na salt Sodium citrate 5.00 5.00 5.00 5.00 Optic brightener0.10 0.10 0.10 0.10 Sodium sulfate 17.00 17.00 17.00 17.00 Fillers,water, minors balance to 100%

EXAMPLE XX

Granular Fabric Cleaning Compositions Example No. Components A B Linearalkyl benzene sulphonate 11.4 10.70 Tallow alkyl sulphate 1.80 2.40C₁₄₋₁₅ alkyl sulphate 3.00 3.10 C₁₄₋₁₅ alcohol 7 times ethoxylated 4.004.00 Tallow alcohol 11 times ethoxylated 1.80 1.80 Dispersant 0.07 0.1Silicone fluid 0.80 0.80 Trisodium citrate 14.00 15.00 Citric acid 3.002.50 Zeolite 32.50 32.10 Maleic acid acrylic acid copolymer 5.00 5.00Diethylene triamine penta methylene 1.00 0.20 phosphonic acidPolysaccharide 1 3 Protease 0.1 0.01 Lipase 0.36 0.40 Amylase 0.30 0.30Sodium silicate 2.00 2.50 Sodium sulphate 3.50 5.20 Polyvinylpyrrolidone 0.30 0.50 Perborate 0.5 1 Phenol sulphonate 0.1 0.2Peroxidase 0.1 0.1 Minors Up to 100 Up to 100

EXAMPLE XXI

Granular Fabric Cleaning Compositions Example No. Components A B Sodiumlinear C₁₂ alkyl benzene-sulfonate 6.5 8.0 Sodium sulfate 15.0 18.0Zeolite A 26.0 22.0 Sodium nitrilotriacetate 5.0 5.0 Polyvinylpyrrolidone 0.5 0.7 Tetraacetylethylene diamine 3.0 3.0 Boric acid 4.0 —Perborate 0.5 1 Phenol sulphonate 0.1 0.2 Polysaccharide 2 0.5 Protease0.02 0.05 Fillers (e.g., silicates; carbonates; perfumes; Up to 100 Upto 100 water)

EXAMPLE XXII

Compact Granular Fabric Cleaning Composition Components Weight % AlkylSulphate 8.0 Alkyl Ethoxy Sulphate 2.0 Mixture of C25 and C45 alcohol 3and 7 times ethoxylated 6.0 Polyhydroxy fatty acid amide 2.5 Zeolite17.0 Layered silicate/citrate 16.0 Carbonate 7.0 Maleic acid acrylicacid copolymer 5.0 Soil release polymer 0.4 Carboxymethyl cellulose 0.4Poly (4-vinylpyridine)-N-oxide 0.1 Copolymer of vinylimidazole andvinylpyrrolidone 0.1 PEG2000 0.2 Polysaccharide Protease 0.03 Lipase 0.2Cellulase 0.2 Tetracetylethylene diamine 6.0 Percarbonate 22.0 Ethylenediamine disuccinic acid 0.3 Suds suppressor 3.5 Disodium-4,4′-bis(2-morpholino-4-anilino-s-triazin-6- 0.25 ylamino)stilbene-2,2′-disulphonate Disodium-4,4′-bis (2-sulfostyril) biphenyl0.05 Water, Perfume and Minors Up to 100

EXAMPLE XXIII

Granular Fabric Cleaning Composition Components Weight % Linear alkylbenzene sulphonate 7.6 C₁₆-C₁₈ alkyl sulfate 1.3 C₁₄₋₁₅ alcohol 7 timesethoxylated 4.0 Coco-alkyl-dimethyl hydroxyethyl ammonium chloride 1.4Dispersant 0.07 Silicone fluid 0.8 Trisodium citrate 5.0 Zeolite 4A 15.0Maleic acid acrylic acid copolymer 4.0 Diethylene triamine pentamethylene phosphonic acid 0.4 Perborate 15.0 Tetraacetylethylene diamine5.0 Smectite clay 10.0 Poly (oxyethylene) (MW 300,000) 0.3Polysaccharide 0.8 Protease 0.02 Lipase 0.2 Amylase 0.3 Cellulase 0.2Sodium silicate 3.0 Sodium carbonate 10.0 Carboxymethyl cellulose 0.2Brighteners 0.2 Water, perfume and minors Up to 100

EXAMPLE XXIV

Granular Fabric Cleaning Composition Components Weight % Linear alkylbenzene sulfonate 6.92 Tallow alkyl sulfate 2.05 C₁₄₋₁₅ alcohol 7 timesethoxylated 4.4 C₁₂₋₁₅ alkyl ethoxy sulfate - 3 times ethoxylated 0.16Zeolite 20.2 Citrate 5.5 Carbonate 15.4 Silicate 3.0 Maleic acid acrylicacid copolymer 4.0 Carboxymethyl cellulase 0.31 Soil release polymer0.30 Polysaccharide 0.5 Protease 0.1 Lipase 0.36 Cellulase 0.13Perborate tetrahydrate 11.64 Perborate monohydrate 8.7Tetraacetylethylene diamine 5.0 Diethylene tramine penta methylphosphonic acid 0.38 Magnesium sulfate 0.40 Brightener 0.19 Perfume,silicone, suds suppressors 0.85 Minors Up to 100

EXAMPLE XXV

Granular Fabric Cleaning Composition Component A B C Base GranuleComponents LAS/AS/AES (65/35) 9.95 — — LAS/AS/AES (70/30) — 12.05 7.70Alumino silicate 14.06 15.74 17.10 Sodium carbonate 11.86 12.74 13.07Sodium silicate 0.58 0.58 0.58 NaPAA Solids 2.26 2.26 1.47 PEG Solids1.01 1.12 0.66 Brighteners 0.17 0.17 0.11 DTPA — — 0.70 Sulfate 5.466.64 4.25 DC-1400 Deaerant 0.02 0.02 0.02 Moisture 3.73 3.98 4.33 Minors0.31 0.49 0.31 B.O.T. Spray-on Nonionic surfactant 0.50 0.50 0.50Agglomerate Components LAS/AS (25/75) 11.70 9.60 10.47 Alumino silicate13.73 11.26 12.28 Carbonate 8.11 6.66 7.26 PEG 4000 0.59 0.48 0.52Moisture/Minors 4.88 4.00 4.36 Functional Additives Sodium carbonate7.37 6.98 7.45 Perborate 1.03 1.03 2.56 TAED — 1.00 — NOBS — — 2.40 Soilrelease polymer 0.41 0.41 0.31 Polysaccharide 1 0.75 3 Cellulase 0.330.33 0.24 Protease 0.1 0.05 0.15 AE-Flake 0.40 0.40 0.29 Liquid Spray-onPerfume 0.42 0.42 0.42 Noionic spray-on 1.00 1.00 0.50 Minors Up to 100

EXAMPLE XXVI

Granular Fabric Cleaning Composition A B Surfactant Na LAS 6.40 — KLAS —9.90 AS/AE3S 6.40 4.39 TAS 0.08 0.11 C24AE5 3.48 — Genagen — 1.88N-cocoyl N-methyl 1.14 2.82 glucamine (lin) C₈₋₁₀ dimethyl 1.00 1.40hydroxyethyl ammonium chloride Builder Zeolite 20.59 13.39 SKS-6 10.8410.78 Citric Acid 2.00 2.00 Buffer Carbonate 9.60 12.07 Bicarbonate 2.002.00 Sulphate 2.64 — Silicate 0.61 0.16 Polymer Acrylic acid/maleic 1.171.12 acid copolymer (Na) Carboxymethyl 0.45 0.24 cellulose Polymer 0.340.18 Hexamethylene- 1.00 1.00 diamine tetra-E24 ethoxylate,diquaternized with methyl chloride Enzyme Protease 0.03 0.03 (% pureenzyme) Cellulase 0.26 0.26 Amylase 0.65 0.73 Lipase 0.27 0.15 BleachTAED (100%) 3.85 3.50 Phenolsulfonate — 2.75 ester of N-nonanoyl-6-aminocaproic acid Percarbonate 16.20 18.30 HEDP 0.48 0.48 EDDS 0.30 0.30Miscellaneous Polysaccharide 1 2 Malic particle 2.20 + bicarb Brightener15/49 0.077/0.014 0.07/0.014 Zinc phthalocyanine 0.0026 0.0026 sulfonatePolydimethylsiloxane 0.25 0.24 with trimethylsilyl end blocking unitsSoap — 1.00 Perfume 0.45 0.55 TOTAL 100 100

EXAMPLE XXVII

Granular Fabric Cleaning Composition A B Surfactant NaLAS 6.8 0.4 KLAS —10.9 FAS 0.9 0.1 AS 0.6 1.5 C25AE3S 0.1 — AE5 4.2 — N-Cocoyl-N-MethylGlucamine — 1.8 Genagen — 1.2 C₈₋₁₀ dimethyl hydroxyethyl — 1.0 ammoniumchloride Builder SKS-6 3.3 9.0 Zeolite 17.2 18.9 Citric Acid 1.5 —Buffer Carbonate 21.1 15.0 Sodium Bicarbonate — 2.6 Sulphate 15.2 5.5Malic Acid — 2.9 Silicate 0.1 — Polymer Acrylic acid/maleic acidcopolymer 2.2 0.9 (Na) Hexamethylene-diamine tetra-E24 0.5 0.7ethoxylate, diquaternized with methyl chloride Polymer 0.1 0.1 CMC 0.20.1 Enzymes Protease (% pure enzyme) 0.02 0.05 Lipase 0.18 0.14 Amylase0.64 0.73 Cellulase 0.13 0.26 Bleach TAED 2.2 2.5 Phenolsulfonate esterof N-nonanoyl- — 1.96 6-aminocaproic acid Sodium Percarbonate — 13.1 PB415.6 — EDDS 0.17 0.21 MgSO₄ 0.35 0.47 HEDP 0.15 0.34 MiscellaneousPolysaccharide 2 1 Brightener 0.06 0.04 Zinc phthalocyanine sulfonate0.0015 0.0020 Polydimethylsiloxane with 0.04 0.14 trimethylsilyl endblocking units Soap 0.5 0.7 Perfume 0.35 0.45 Speckle 0.5 0.6

EXAMPLE XXVIII

The following granular laundry detergent compositions XXVIII A-C are ofparticular utility under European machine wash conditions were preparedin accord with the invention:

Component A B C LAS 7.0 5.61 4.76 TAS — — 1.57 C45AS 6.0 2.24 3.89C25E3S 1.0 0.76 1.18 C45E7 — 2.0 C25E3 4.0 5.5 — QAS 0.8 2.0 2.0 STPP —— Zeolite A 25.0 19.5 19.5 Citric acid 2.0 2.0 2.0 NaSKS-6 8.0 10.6 10.6Carbonate I 8.0 10.0 8.6 MA/AA 1.0 2.6 1.6 CMC 0.5 0.4 0.4 PB4 — 12.7 —Percarbonate — — 19.7 TAED 3.1 5.0 Citrate 7.0 — — DTPMP 0.25 0.2 0.2HEDP 0.3 0.3 0.3 QEA 1 0.9 1.2 1.0 Polysaccharide 0.5 0.2 1 Protease0.02 0.05 0.035 Lipase 0.15 0.25 0.15 Cellulase 0.28 0.28 0.28 Amylase0.4 0.7 0.3 PVPI/PVNO 0.4 — 0.1 Photoactivated bleach (ppm) 15 ppm 27ppm 27 ppm Brightener 1 0.08 0.19 0.19 Brightener 2 — 0.04 0.04 Perfume0.3 0.3 0.3 Effervescent granules (malic acid 15 15 5 40%, sodiumbicarbonate 40%, sodium carbonate 20%) Silicone antifoam 0.5 2.4 2.4Minors/inerts to 100%

EXAMPLE XXIX

The following formulations are examples of compositions in accordancewith the invention, which may be in the form of granules or in the formof a tablet.

Component XXIX C45 AS/TAS 3.0 LAS 8.0 C25 AE3S 1.0 NaSKS-6 9.0 C25AE5/AE3 5.0 Zeolite A 10.0 SKS-6 (I) (dry add) 2.0 MA/AA 2.0 Citric acid1.5 EDDS 0.5 HEDP 0.2 PB1 10.0 NACA OBS 2.0 TAED 2.0 Carbonate 8.0Sulphate 2.0 Polysaccharide 5 Amylase 0.3 Lipase 0.2 Protease 0.02Minors (Brightener/SRP1/ 0.5 CMC/Photobleach/MgSO₄/ PVPVI/Sudssuppressor/ PEG) Perfume 0.5

EXAMPLE XXX

Granular laundry detergent compositions XXX A-E are of particularutility under Japanese machine wash conditions and are prepared inaccordance with the invention:

Component A B C D E LAS 23.57 23.57 21.67 21.68 21.68 FAS 4.16 4.16 3.833.83 3.83 Nonionic surfactant 3.30 3.30 2.94 3.27 3.27 Bis(hydroxyethyl) 0.47 0.47 1.20 1.20 1.20 methyl alkyl ammonium chlorideSKS-6 7.50 7.50 5.17 5.76 5.06 Polyacrylate copolymer 7.03 7.03 14.3614.36 14.36 (MW 11000) (maleic/ acrylate ratio of 4:6) Zeolite 11.9011.40 10.69 11.34 11.34 Carbonate 14.90 14.82 11.71 11.18 11.18 Silicate12.00 12.00 12.37 12.38 12.38 Polysaccharide 5 2 1 0.4 0.6 Protease0.016 0.016 0.046 0.046 0.046 Lipase — — 0.28 — — Amylase — — 0.62 — —Cellulase — — 0.48 — 0.70 NOBS 3.75 3.75 2.70 2.70 2.70 PB1 3.53 — 2.60— — Sodium percarbonate — 4.21 — 3.16 3.16 SRP 0.52 0.52 0.70 0.70 0.70Brightener 0.31 0.31 0.28 0.28 0.50 AE-coflake 0.17 0.20 0.17 0.17 0.17Polydimethylsiloxane — — 0.68 0.68 0.68 Perfume 0.06 0.06 0.08 — —Perfume — — — 0.23 0.23 Hydrophobic precipitated 0.30 0.30 0.30 0.300.30 silica PEG4000 0.19 0.19 0.17 0.17 0.17 Minors/inerts to 100%

EXAMPLE XXXI

Liquid Fabric Cleaning Compositions Example No. Component A B C D EPolysaccharide 0.5 1 2 5 1 Protease 0.05 0.03 0.30 0.03 0.10 C₁₂-C₁₄alkyl sulfate, Na 20.00 20.00 20.00 20.00 20.00 2-Butyl octanoic acid5.00 5.00 5.00 5.00 5.00 Sodium citrate 1.00 1.00 1.00 1.00 1.00 C₁₀alcohol ethoxylate (3) 13.00 13.00 13.00 13.00 13.00 Monethanolamine2.50 2.50 2.50 2.50 2.50 Water/propylene glycol/ethanol balance to 100%(100:1:1)

EXAMPLE XXXII

Liquid Fabric Cleaning Compositions Example No. Component A B C₁₂₋₁₄alkenyl succinic acid 3.0 8.0 Citric acid monohydrate 10.0 15.0 SodiumC₁₂₋₁₅ alkyl sulphate 8.0 8.0 Sodium sulfate of C₁₂₋₁₅ alcohol 2 timesethoxylated — 3.0 C₁₂₋₁₅ alcohol 7 times ethoxylated — 8.0 Diethylenetriamine penta (methylene phosphonic acid) 0.2 — Oleic acid 1.8 —Ethanol 4.0 4.0 Propanediol 2.0 2.0 Polysaccharide 1 2 Protease 0.010.02 Polyvinyl pyrrolidone 1.0 2.0 Suds suppressor 0.15 0.15 NaOH up topH 7.5 Perborate 0.5 1 Phenol sulphonate 0.1 0.2 Peroxidase 0.4 0.1Waters and minors up to 100%

EXAMPLE XXXIII

Liquid Fabric Cleaning Compositions Example No. Component 40 NaLAS (100%am) 16 Neodol 21.5 Citrate 6.8 EDDS 1.2 Dispersant 1.3 Perborate 12Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid 6 Polysaccharide0.5 Protease (% pure enzyme) 0.03 Amylase 0.40 Cellulase 0.03 Solvent(BPP) 18.5 Polymer 0.1 Carbonate 10 FWA 15 0.2 TiO₂ 0.5 PEG 8000 0.4Perfume 1.0-1.2 Suds suppressor 0.06 Waters and minors up to 100%

EXAMPLE XXXIV

Liquid Fabric Cleaning Compositions Example No. Component A B D1 H₂O38.63 — MEA 0.48 9.0 NaOH 4.40 1.0 Pdiol 4.00 10.0 Citric acid 2.50 2.0Sodium sulfate 1.75 — DTPA 0.50 1.0 FWA Premix (Br 15/MEA/N1 23-9) 0.150.15 Na C25AE1.80S 23.50 — AE3S (11) — 4.0 C11.8HLAS 3.00 14.0 Neodol2.00 6.0 EtOH 0.50 2.0 Ca*Formate 0.10 0.1 Borax premix(Borax/MEA/Pdiol/Citric Acid) 2.50 — Boric acid — 1.0 C10 APA 1.50 —TEPA 105 1.20 — FA C12-18 5.00 — Neptune LC 0.50 — Dye 0.0040 0.0015Polysaccharide 1 0.7 Cellulase 0.053 0.2 Amylase 0.15 0.2 Protease 0.10.1 DC 2-3597 0.12 0.2 Rapeseed FA 6.50 4.0 Waters and minors up to 100%

EXAMPLE XXXV

Liquid Fabric Cleaning Composition Component XXXV NaOH 5.50 Pdiol 6.90Citric acid 1.50 DTPA 1.50 FWA Premix (Br 15/MEA/N1 23-9) 0.15 AE3S (H)2.50 LAS (H) 13.0 Neodol 2.00 EtOH 3.50 Ca*Formate 0.10 Boric acid 1.00Clay 4.00 Polysaccharide 2 Amylase 0.15 Protease 0.02 Fatty Acid 16.50Waters and minors up to 100%

EXAMPLE XXXVI

Liquid Fabric Cleaning Composition Liquid fabric cleaning composition ofparticular utility under Japanese machine wash conditions is prepared inaccordance with the invention: Component XXXVI AE2.5S 15.00 AS 5.50N-Cocoyl N-methyl glucamine 5.00 Nonionic surfactant 4.50 Citric acid3.00 Fatty acid 5.00 Base 0.97 Monoethanolamine 5.10 1,2-Propanediol7.44 EtOH 5.50 HXS 1.90 Boric acid 3.50 Ethoxylated tetraethylene- 3.00pentaimine SRP 0.30 Polysaccharide 1 Protease 0.069 Amylase 0.06Cellulase 0.08 Lipase 0.18 Brightener 0.10 Minors/inerts to 100%

EXAMPLE XXXVII

Liquid Fabric Cleaning Composition Liquid fabric cleaning composition ofparticular utility under Japanese machine wash conditions and for finefabrics is prepared in accordance with the invention: Component XXXVIIAE2.5S 2.16 AS 3.30 N-Cocoyl N-methyl glucamine 1.10 Nonionic surfactant10.00 Citric acid 0.40 Fatty acid 0.70 Base 0.85 Monoethanolamine 1.011,2-Propanediol 1.92 EtOH 0.24 HXS 2.09 Polysaccharide 2 Protease 0.01Amylase 0.06 Minors/inerts to 100%

EXAMPLE XXXVIII

Bar Fabric Cleaning Compositions Example No. Component A B C DPolysaccharide 0.5 2 5 3 Protease 0.3 0.05 0.1 0.02 C₁₂-C₁₆ alkylsulfate, Na 20.0 20.0 20.0 20.00 C₁₂-C₁₄ N-methyl glucamide 5.0 5.0 5.05.00 C₁₁-C₁₃ alkyl benzene sulfonate, Na 10.0 10.0 10.0 10.00 Sodiumpyrophosphate 7.0 7.0 7.0 7.00 Sodium tripolyphosphate 7.0 7.0 7.0 7.00Zeolite A (0.1-.10μ) 5.0 5.0 5.0 5.00 Carboxymethylcellulose 0.2 0.2 0.20.20 Polyacrylate (MW 1400) 0.2 0.2 0.2 0.20 Coconut monethanolamide 5.05.0 5.0 5.00 Brightener, perfume 0.2 0.2 0.2 0.20 CasO₄ 1.0 1.0 1.0 1.00MgSO₄ 1.0 1.0 1.0 1.00 Water 4.0 4.0 4.0 4.00 Filler* balance to 100%*Can be selected from convenient materials such as CaCO₃, talc, clay,silicates, and the like.

The compositions of the present invention can be suitably prepared byany process chosen by the formulator, non-limiting examples of which aredescribed in U.S. Pat. No. 5,691,297 Nassano et al., issued Nov. 11,1997; U.S. Pat. No. 5,574,005 Welch et al., issued Nov. 12, 1996; U.S.Pat. No. 5,569,645 Dinniwell et al., issued Oct. 29, 1996; U.S. Pat. No.5,565,422 Del Greco et al., issued Oct. 15, 1996; U.S. Pat. No.5,516,448 Capeci et al., issued May 14, 1996; U.S. Pat. No. 5,489,392Capeci et al., issued Feb. 6, 1996; U.S. Pat. No. 5,486,303 Capeci etal., issued Jan. 23, 1996 all of which are incorporated herein byreference.

In addition to the above examples, the cotyledon extracts of the presentinvention can be formulated into any suitable laundry detergentcomposition, non-limiting examples of which are described in U.S. Pat.No. 5,679,630 Baeck et al., issued Oct. 21, 1997; U.S. Pat. No.5,565,145 Watson et al., issued Oct. 15, 1996; U.S. Pat. No. 5,478,489Fredj et al., issued Dec. 26, 1995; U.S. Pat. No. 5,470,507 Fredj etal., issued Nov. 28, 1995; U.S. Pat. No. 5,466,802 Panandiker et al.,issued Nov. 14, 1995; U.S. Pat. No. 5,460,752 Fredj et al., issued Oct.24, 1995; U.S. Pat. No. 5,458,810 Fredj et al., issued Oct. 17, 1995;U.S. Pat. No. 5,458,809 Fredj et al., issued Oct. 17, 1995; U.S. Pat.No. 5,288,431 Huber et al., issued Feb. 22, 1994 all of which areincorporated herein by reference.

Having described the invention in detail with reference to preferredembodiments and the examples, it will be clear to those skilled in theart that various changes and modifications may be made without departingfrom the scope of the invention and the invention is not to beconsidered limited to what is described in the specification.

What is claimed is:
 1. A starch-free treating composition for treating afabric in need of treatment comprising a polysaccharide having a degreeof polymerization in the range of from about 40 to about 100,000 and asecond material selected from the group consisting of a derivatizedpolysaccharide, an oligosaccharide, a monosaccharide, and mixturesthereof.
 2. The composition according to claim 1, wherein saidpolysaccharide has a molecular weight in the range of from about 10,000to about 10,000,000.
 3. The composition according to claim 1, whereinsaid polysaccharide is selected from the group consisting of gums,arabinans, galactans, seeds and mixtures thereof.
 4. The compositionaccording to claim 1, wherein said polysaccharide is present in saidtreating composition at a level of from about 0.01% to about 25% byweight of said treating composition.
 5. The composition according toclaim 1, wherein said composition further comprises one or moreingredients selected from the group consisting of surfactants, builders,bleaching agents, dye transfer inhibiting agents, chelants, dispersants,polysaccharides, softening agents, suds suppressors, carriers, enzymes,enzyme stabilizing systems, polyacids, soil removal agents,anit-redoposition agents, hydrotropes, opacifiers, antioxidants,bactericides, dyes, perfumes, brighteners, anti-encrustation agents andmixtures thereof.
 6. The composition according to claim 1, wherein saidcomposition comprises a derivatized polysaccharide selected from thegroup consisting of amino alginates, O-methyl-(N-1,12-dodecanediamine)cellulose, biotin heparin, carboxymethylated dextran, guarpolycarboxylic acid, carboxymethylated locust bean gum, caroxymethylatedxanthan, carboxymethylated pachyman, chitosan phosphate, chitosanphosphate sulfate, diethylaminoethyl dextran, dodecylamide alginate andmixtures thereof.
 7. The composition according to claim 1, wherein saidcomposition comprises an oligosaccharide, said oligosaccharidecomprising a degree of polymerization of less than about 20 and one ormore monosaccharides selected from the group consisting of glucose,fructose, galactose, zylose, mannose, arabinose, rhamnose, ribose,lyxose, allose, altrose, gulose, idose, talose and their derivatives. 8.A method of treating a fabric in need of treatment comprising contactingsaid fabric with an effective amount of a polysaccharide-containingtreating composition according to claim
 1. 9. The method according toclaim 8, wherein said fabric is imparted color appearance and/or pillprevention and/or abrasion resistance and/or wrinkle resistance and/orshrinkage resistance properties following treatment via said method. 10.The method according to claim 8, wherein said polysaccharide-containingtreating composition further comprises one or more cleaning adjunctmaterials selected from the group consisting of surfactants, builders,bleaching agents, dye transfer inhibiting agents, chelants, dispersants,polysaccharides, softening agents, suds suppressors, carriers, enzymes,enzyme stabilizing systems, polyacids, soil removal agents,anti-redeoposition agents, hydrotropes, opacifiers, antioxidants,bactericides, dyes, perfumes, brighteners and mixtures thereof.
 11. Themethod according to claim 8, wherein said polysaccharide-containingtreating composition is applied to said fabric via a spray dispenser.12. A fabric treated with the method according to claim
 8. 13. Atreating composition for treating a fabric in need of treatment, saidcomposition comprising: A) a polysaccharide having a degree ofpolymerization of over 40; B) at least one of the following material: aderivatized polysaccharide, an oligosaccharide and one or moremonosaccharides; C) one or more cleaning adjunct materials selected fromthe group consisting of: builders, bleaching agents, dye transferinhibiting agents, chelants, dispersants, polysaccharides, softeningagents, suds suppressors, carriers, enzymes, enzyme stabilizing systems,polyacids, soil removal agents, anti-redeoposition agents, hydrotropes,opacifiers, antioxidants, bactericides, dyes, perfumes, brighteners andmixtures thereof; and D) optionally, a surfactant.